High melt strength polymers and method of making same

ABSTRACT

A process of making a polymer is described. The process includes contacting one or more olefinic monomers in the presence of at least a high molecular weight (HMW) catalyst and at least a low molecular weight (LMW) catalyst in a polymerization reactor system; and effectuating the polymerization of the one or more olefinic monomers in the polymerization reactor system to obtain an olefin polymer, wherein the LMW catalyst has an R v   L , defined as  
         R   v   L     =       [   vinyl   ]         [   vinyl   ]     +     [   vinylidene   ]     +     [   cis   ]     +     [   trans   ]             
wherein [vinyl] is the concentration of vinyl groups in the olefin polymer produced by the low molecular weight catalyst expressed in vinyls/1,000 carbon atoms; [vinylidene], [cis] and [trans] are the concentration of vinylidene, cis and trans groups in the olefin polymer expressed in the number of the respective groups per 1,000 carbon atoms, of greater than 0.12, and wherein the HMW catalyst has a reactivity ratio, r1 of about 5 or less.

PRIOR RELATED APPLICATIONS

This application claims priority to prior filed U.S. Provisional PatentApplication Ser. No. 60/276,719, filed on Mar. 16, 2001, which isincorporated by reference herein in its entirety.

FEDERALLY SPONSORED RESEARCH STATEMENT

Not applicable.

REFERENCE TO MICROFICHE APPENDIX

Not applicable.

FIELD OF THE INVNON

This invention relates to polyolefins with improved properties andmethods of making the polyolefins.

BACKGROUND OF TBE INVENTION

Ethylene homopolymers and copolymers are a well-known class of olefinpolymers from which various plastic products are produced. Such productsinclude films, fibers, coatings, and molded articles; such as containersand consumer goods. The polymers used to make these articles areprepared from ethylene, optionally with one or more copolymerizablemonomers. There are many types of polyethylene. For example, low densitypolyethylene (“LDPE”) is generally produced by free radicalpolymerization and consists of highly branched polymers with long andshort chain branches distributed throughout the polymer. However, filmsof LDPE have relatively low toughness, low puncture resistance, lowtensile strength, and poor tear properties, compared to linear-lowdensity polyethylene (“LLDPE”). Moreover, the cost to manufacture LDPEis relatively high because it is produced under high pressures (e.g., ashigh as 45,000 psi) and high temperatures. Most LDPE commercialprocesses have a relatively low ethylene conversion. As such, largeamounts of unreacted ethylene must be recycled and repressurized,resulting in an inefficient process with a high energy cost.

A more economical process to produce polyethylene involves use of acoordination catalyst, such as a Ziegler-Natta catalyst, under lowpressures. Conventional Ziegler-Natta catalysts are typically composedof many types of catalytic species,. each having different metaloxidation states and different coordination environments with ligands.Examples of such heterogeneous systems are known and include metalhalides activated by an organometallic co-catalyst, such as titaniumchloride supported on magnesium chloride, activated with trialkylaluminum. Because these systems contain more than one catalytic species,they possess polymerization sites with different activities and varyingabilities to incorporate comonomer into a polymer chain. Theconsequenceof such multi-site chemistry is a product with poor controlof the polymer chain architecture, when compared to a neighboring chain.Moreover, differences in the individual catalyst site produce polymersof high molecular weight at some sites and low molecular weight atothers, resulting in a polymer with a broad molecular weightdistribution and a heterogeneous composition. Consequently, themolecular weight distribution of such polymers is fairly broad asindicated by M_(w)/M_(n) (also referred to as polydispersity index or“PDI” or “MWD”) Due to the heterogeneity of the composition, theirmechanical and other properties are less desirable.

Recently, a new catalyst technology useful in the polymerization ofolefins has been introduced. It is based on the chemistry of single-sitehomogeneous catalysts, including metallocenes which are organometalliccompounds containing one or more cyclopentadienyl ligands attached to ametal, such as hafnium, titanium, vanadium, or zirconium. A co-catalyst,such as oligomeric methyl alumoxane, is often used to promote thecatalytic activity of the catalyst. By varying the metal component andthe substituents on the cyclopentadienyl ligand, a myriad of polymerproducts may be tailored with molecular weights ranging from about 200to greater than 1,000,000 and molecular weight distributions from 1.0 toabout 15. Typically, the molecular weight distribution of a metallocenecatalyzed polymer is less than about 3, and such a polymer is consideredas a narrow molecular weight distribution polymer.

The uniqueness of metallocene catalysts resides, in part, in the stericand electronic equivalence of each active catalyst molecule.Specifically, metallocenes are characterized as having a single, stablechemical site rather than a mixture of sites as discussed above forconventional Ziegler-Natta catalysts. The resulting system is composedof catalysts which have a singular activity and selectivity. For thisreason, metallocene catalyst systems are often referred to as “singlesite” owing to their homogeneous nature. Polymers produced by suchsystems are often referred to as single site resins in the art.

With the advent of coordination catalysts for ethylene polymerization,the degree of long-chain branching in an ethylene polymer wassubstantially decreased, both for the traditional Ziegler-Natta ethylenepolymers and the newer metallocene catalyzed ethylene polymers. Both,particularly the metallocene copolymers, are substantially linearpolymers with a limited level of long chain branching or linearpolymers. These polymers are relatively difficult to melt process whenthe molecular weight distribution is less than about 3.5. Thus, adilemma appears to exist—polymers with a broad molecular weightdistribution are easier to process but may lack desirable solid stateattributes otherwise available from metallocene catalyzed copolymers. Onthe contrary, linear or substantially linear polymers catalyzed by ametallocene catalyst have desirable physical properties in the solidstate but may nevertheless lack the desired processability when in themelt.

In blown film extrusion, the bubble stability is a relatively importantprocess parameter. If the melt strength of the polymer is too low, thebubble is not stable and thus affects the film quality. Therefore, it isdesirable to produce polymers with relatively high melt strength. Forthese reasons, there is a need for a polymer and polymerizationprocesses which could produce a polymer with melt processingcharacteristics similar to or better than LDPE (i.e., high meltstrength) while exhibiting solid state properties comparable to ametallocene-catalyzed polymer.

SUMMARY OF THE INVENTION

Embodiments of the invention provide a process of making a polymercomprising (a) contacting one or more olefinic monomers in the presenceof at least a high molecular weight (HMW) catalyst and at least a lowmolecular weight (LMW) catalyst in a polymerization reactor system; and(b) effectuating the polymerization of the one or more olefinic monomersin the polymerization reactor system to obtain an olefin polymer,wherein the LMW catalyst has an R_(v) ^(L), defined as$R_{v}^{L} = \frac{\lbrack{vinyl}\rbrack}{\lbrack{vinyl}\rbrack + \lbrack{vinylidene}\rbrack + \lbrack{cis}\rbrack + \lbrack{trans}\rbrack}$wherein [vinyl] is the concentration of vinyl groups in the olefinpolymer produced by the low molecular weight catalyst expressed invinyls/1,000 carbon atoms; [vinylidene], [cis] and [trans] are theconcentration of vinylidene, cis and trans groups in the olefin polymerexpressed in the number of the respective groups per 1,000 carbon atoms,of greater than 0.12, and wherein the HMW catalyst has a reactivityratio, r₁ of about 5 or less. In other embodiments. the low molecularweight catalyst has an R_(v) ^(L) value that is greater than about 0.45,or greater than about 0.50. The high molecular weight catalyst of someembodiments has a reactivity ratio, r₁ that is about 4 or less, or about3 or less. Some processes of the invention comprises catalyst pairs inwhich the R_(v) ^(L)/R_(v) ^(H) ratio is about 0.80 to about 1.40.

In some embodiments of the process the high molecular weight catalysthas an R_(v) ^(H) defined as$R_{v}^{H} = \frac{\lbrack{vinyl}\rbrack}{\lbrack{vinyl}\rbrack + \lbrack{vinylidene}\rbrack + \lbrack{cis}\rbrack + \lbrack{trans}\rbrack}$wherein [vinyl] is the concentration of vinyl groups in the olefinpolymer produced by the low molecular weight catalyst expressed invinyls/1,000 carbon atoms; [vinylidene], [cis] and [trans] are theconcentration of vinylidene, cis and trans groups in the olefin polymerexpressed in the number of the respective groups per 1,000 carbon atoms,and wherein a ratio of R_(v) ^(L)/R_(v) ^(H) ranges from 0.5 to about2.0. In some processes R_(v) ^(L) is greater than about 0.15, greaterthan about 0.20, greater than about 0.25, or greater than about 0.35.

Polymerization reactions may be carried out under continuous solutionpolymerization conditions, or as a slurry process. In some embodiments,the high molecular weight catalyst or the low molecular weight catalystor a combination thereof are supported on an inert support. Somepolymerization reactions may be performed in a polymerization reactorsystem includes a first reactor connected to a second reactor inparallel so that mixing occurs in a third reactor. In some processes,the HMW catalyst contacts the one or more olefin monomers in the firstreactor to produce a first reactor product and the LMW catalyst contactsthe first reactor product in the second reactor.

In some embodiments, the first reactor is connected to the secondreactor in series and the HMW catalyst contacts the one or more olefinmonomers in the first reactor to produce a first reactor product and theLMW catalyst contacts the first reactor product in the second reactor.In other processes, the HMW catalyst, the LMW catalyst, and the one ormore olefinic monomers are sequentially introduced into thepolymerization reactor system.

Other embodiments of the invention disclose a polymer composition. Insome embodiments the polymer composition comprises (a) a backbone chainand (b) a plurality of long chain branches connected to the backbone;wherein the value of ²g′_(LCB)−¹g′_(LCB) of less than 0.22, where¹g′_(LCB) is the long chain branching index for a fraction of thecomposition having a M_(w) of 100,000 and ²g′_(LCB) is the long chainbranching index for a fraction of the composition having a M_(w) of500,000.

Some polymer compositions herein comprise (a) a high molecular weight(HMW), branched component and (b) a low molecular weight (LMW), branchedcomponent wherein the composition is substantially free of short chainbranches characteristic of LDPE and characterized by a melt strength(MS) that satisfies the following relationship:${MS} \geq {\frac{x}{I_{2}} + y}$where x is greater than or equal to about 12.5 and y is greater than orequal to about 3 are described.

In other embodiments, polymers comprise (a) a high molecular weight(HMW), branched component; and (b) a low molecular weight (LMW),branched component wherein the composition is substantially free ofshort chain branches characteristic of LDPE and characterized by a meltstrength (MS) that satisfies the melt strength formula described abovewhere x is greater than or equal to about 3 and y is greater than orequal to about 4.5 and have a molecular weight distribution of greaterthan 3.

In some embodiments, the disclosed polymers have a melt strength thatfollows the formula wherein x is greater or equal to than about 12.5 andy is greater than or equal to about 4.5. In other embodiments x isgreater than about 15 and y is greater than or equal to about 4.5. Stillother compositions have a melt strength that is greater than the formulax is greater than or equal to about 20 and y is greater than or equal toabout 7.5. In other embodiments the melt strength follows the formulawherein x is greater than about 5 and y is greater than or equal toabout 4.5, wherein x is greater than about 7.5 and y is greater than orequal to about 4.5, or wherein x is greater than about 9.5 and y isgreater than or equal to about 7.

Some polymers have a value of ²g′_(LCB)−¹g′_(LCB) is less than or equalto about 0.20, less than or equal to 0.15, or less than or equal to0.12. Some such polymers follow one or more of the above described meltstrength relationships, while others may not. Additionally somecompositions have a molecular weight distribution from greater than 3.0to about 12.0. In some embodiments the molecular weight distribution ofthe composition includes a high molecular weight (HMW) component and alow molecular weight (LMW) component. In some compositions, the HMWcomponent, the LMW component, or both have a molecular weightdistributions of about 1.5 to about 4.0. In some embodiments, thepolymers include a HMW component with a molecular weight distribution ofless than about 3.0. and a LMW component has a molecular weightdistribution of less than about 3.0 In some embodiments, the compositionincludes a HMW component and a LMW component that have substantiallyequal amounts of comonomer incorporation. Some embodiments other thedisclosed compositions have a ratio of the molecular weight of the HMWcomponent to the molecular weight of the LMW component, M_(w) ^(H)/M_(w)^(L), that is greater than about 10. The HMW component may comprise fromgreater than 0% to about 50% by weight of the total composition and theLMW component comprises from about 50% by weight to less than about 100%by weight of the total composition. Preferably, the HMW componentcomprises from greater than 1% to about 10% by weight of the totalcomposition and the LMW component comprises from about 90% by weight toabout 99% by weight of the total composition. In other embodiments, theHMW component comprises from greater than 2% to about 5% by weight ofthe total composition and the LMW component comprises from about 95% byweight to about 98% by weight of the total composition.

In some embodiments, the composition has a HMW component that has aM_(w) greater than about 300,000 g/mol while the LMW component, in somecompositions has a M_(w) less than about 200,000. Other compositions mayhave a HMW component or LMW component greater or less than these values.Some compositions are characterized by a degree of separation, DOS, ofabout 5 or higher while others have a DOS of about 20 or higher, 50orhigher, or 100 or higher. Still other compositions may becharacterized by a DOS of 1000 or higher, 10,000 or higher, or 50000 orhigher.

The polymers described herein may be used for a variety of purposes.Some polymers may be used as films, such as sealant film layers, shrinkfilms, laminating films and stretch films. Some polymers are used asfibers, wires, cables, moldings, or coatings, including rotomoldingsand. extmsion coatings. Some compositions can be used as pipes,profiles, carpet backings, liners, and sacks, such as grocery sacks.Some polymers. are useful as bags or pouches, including bags and pouchesmade by form-fill-seal (FFS) equipment. Some pouches are also fabricatedusing form-fill-seal (FFS) equipment, including vertical form-fill-sealunits.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an imaginary GPC curve illustrating a bimodal molecular weightdistribution.

FIG. 2 shows a GPC spectrum and its deconvoluted peaks for a polymermade in accordance with one embodiment of the invention; and

FIG. 3 is a plot of the melt strength as a function of melt index ofpolymers in accordance with some embodiments of the invention.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or“approximately” is used in connection therewith. They may vary by up to1%, 2%, 5%, or sometimes 10 to 20%. Whenever a numerical range with alower limit, R_(L), and an upper limit R_(U), is disclosed, any number Rfalling within the range is specifically disclosed In particular, thefollowing numbers R within the. range are specifically disclosed:R=R_(L)+k*(R_(U)−R_(L)), wherein k is a variable ranging from 1% to 100%with a 1% increment, i.e. k is 1%, 2%, 3%, 4%, 5%, . . . , 50%, 51%,52%, . . . , 95%, 96%, 97%, 98%, 99%, or 100%. Moreover, any numericalrange defined by two numbers, R, as defined in the above is alsospecifically disclosed.

Embodiments of the invention provide polymer compositions withrelatively high melt strength. In some embodiments, a polymercomposition with relatively high melt strength comprises: (a) a highmolecular weight, branched component and (b) a low molecular weight,branched component wherein the composition is substantially free ofshort chain branches characteristic of LDPE and characterized by a meltstrength (MS) that satisfies the following relationship: $\begin{matrix}{{MS} \geq {\frac{x}{I_{2}} + y}} & (I)\end{matrix}$where I2 is the melt index, x is greater than or equal to 12.5, and y isgreater than or equal to 3. In some embodiments, the value for x in (I)is greater than about 14, greater than about 16, greater than about 20,greater than about 25, or greater than about 30 and the value of y, insome embodiments, is about 4.5, about 5.0, about 6.0, or about 7.0. Inother embodiments, the melt strength is greater than or equal to formula(I) when x is 35 or 40 or y is about 8, about 10, about 15, or about 20.

Some embodiments provide polymer composition comprising: (a) a backbonechain and (b) a plurality of long chain branches connected to thebackbone wherein the composition has a value of g′₂−g′₁ of less than orequal to 0.22, where g′₁ is the branching index for a fraction of thecomposition having a M_(w) of 100,000 and the g′₂ is the branching indexfor a fraction of the composition having a M_(w) of 500,000.

In some embodiments, polymers are characterized by a melt strength (MS)that satisfies the following relationship: $\begin{matrix}{{MS} \geq {\frac{x}{I_{2}} + y}} & ({II})\end{matrix}$where I₂ is the melt index, x is greater than or equal to about 3, and yis greater than or equal to about 4.5 and a molecular weightdistribution of greater than 3. In some embodiments, the value for x in(II) is greater than about 5, greater than about 7, greater than about10, greater than about 12.5, or greater than about 15 and the value ofy, in some embodiments, is about 5.0, about 6.0, or about 7.0.. In otherembodiments, the melt strength is greater than or equal to formula (II)when x is 35 or 40 or y is about 8, about 10, about 15, or about 20. Instill other embodiments, the melt strength may satisfy a formula where xis greater than about any of about 14, about 16, about 20, greater thanabout 25, or about 30 and the value of y, in some embodiments, is about4.5, about 5.0, about 6.0, or about 7.0.

Some polymers are characterized by a melt strength (MS) that satisfiesthe following relationship: $\begin{matrix}{{MS} \geq {\frac{x}{I_{2}} + y}} & ({III})\end{matrix}$where x is greater than or equal to about 3 and y is greater than orequal to about 4.5 and a molecular weight distribution of greater than3.

While certain embodiments possess some polymeric properties that aresnimilar to properties of LDPE (for example, melt strength), the novelpolymers described in the invention can be distinguished from LDPE in anumber of ways. One example of the differences between the novelpolymers described herein and LDPE is the nature of the short-chainbranching. Because LDPE is prepared by radical polymerization in highpressure reactors, the short-chain branches are of varying andcharacteristic lengths. For example, a typicalLDPE with a total of 6-20methyl groups per thousand carbon atoms contains 2-3% methyl, 31-37%ethyl, about 2% propyl, 34-37% butyl, 11-13% amyl (pentyl) as well aslonger branches. The ethyl branches are mostly present as 1,3(predomminantly mcemic) ethyls, or 1,3-ethyls with one ethyl goup on aquaternary carbon; isolated ethyls are rare, as are hexyl groups. Thesedistinctive branching patterns are the result of back-biting of radicalsgenerated during the LDPE polymerization mechanism.

Thus, the novel interpolymers described herein are characterized asbeing substantially free of short-chain branching characteristic ofLDPE. The term “substantially free of short chain branchingcharacteristic of LDPE” means the following. For olefin polymers that donot contain 1-heptene as a (co)monomer, the level of pentyl (otherwiseknown as amyl) branches is less than 0.30 pentyl branches per 1,000total carbon atoms. For olefin polymers that contain 1-heptene(co)monomer (which produces pentyl branches from insertion of the1-heptene) but does not contain 1-hexene (co)monomer, the level of butylbranches is less than 0.6 butyl branches per 1,000 total carbon atoms.For olefin polymers that contain 1-heptene (co)monomer (which producespentyl branches from insertion of the 1-heptene) as well as 1-hexene(co)monomer (which produces butyl branches from insertion of the1-hexene), the level of ethyl branches is less than 0.6 ethyl branchesper 1,000 total carbon atoms. For olefin polymers that contain 1-heptene(co)monomer (which produces pentyl branches from insertion of the1-heptene) as well as 1-hexene (co)monomer (which produces butylbranches from insertion of the 1-hexene), as well as 1-butene(co)monomer (which produces ethyl branches from insertion of the1-butene), the level of propyl branches is less than 0.03 propylbranches per 1,000 total carbon atoms.

It should be understood that one can make blends comprising the polymersaccording to the embodiments of the invention and other polymers,including LDPE. Therefore, it should be understood that the NMR test todetermine if a polymer is “substantially free of short chain branchingcharacteristic of LDPE” should be conducted on the polymer beforeproducing the blend with LDPE.

The polymers described herein also differ from LDPE in that they have arelatively narrow molecular. weight distribution and a controlledlong-chain branch structure; on the other hand, they differ from atypical metallocene catalyzed polymer in that their processability isbetter. Thus, certain of the interpolymers bridge the gap between LDPEand currently available metallocene catalyzed polymers.

The term “polymer” as used herein refers to a macromolecular compoundprepared by polymerizing monomers of the same or a different type. Apolymer refers to homopolymers, copolymers, terpolymers, interpolymers,and so on. The term “interpolymer” used herein refers to polymersprepared by the polymerization of at least two types of monomers orcomonomers. It includes, but is not limited to, copolymers (whichusually refers to polymers prepared from two different monomers orcomonomers), terpolymers (which usually refers to polymers prepared fromthree different types of monomers or comonomers), and tetrapolymers(which usually refers to polymers prepared from four different types ofmonomers or comonomers), and the like.

The term “bimodal” as used herein means that the MWD in a GPC curveexhibits two component polymers wherein one component polymer may evenexist as a hump, shoulder or tail relative to the MWD of the othercomponent polymer. Of course, in some embodiments, a “bimodal molecularweight distribution” may be deconvoluted with the freedom to fit morethan two peaks. In some embodiments, the term “bimodal” does not includemultimodal polymers, such as LDPE. FIG. 1 illustrates an imaginarybimodal MWD and the low molecular weight and high molecular weightcomponents derived from the deconvolution. After deconvolution, the peakwidth at half maxima (WAHM) and the average molecular weight (M_(w)) ofeach component can be obtained. Then the degree of separation (“DOS”)between the two components can be calculated by the following equation:$\begin{matrix}{{DOS} = \frac{M_{w}^{H} - M_{w}^{L}}{{WAHM}^{H} + {WAHM}^{L}}} & ({IV})\end{matrix}$wherein M_(w) ^(H) and M_(w) ^(L) are the respective weight averagemolecular weight of the HMW component and the LMW component; andWAHM^(H) and WAH^(L) are the respective peak width at the half maxima ofthe deconvoluted molecular weight distribution curve for the HMWcomponent and the LMW component. The DOS for the new composition isabout 0.01 or higher. In some embodiments, DOS is higher than about0.05, 0.1, 0.5, or 0.8. Preferably, DOS for the bimodal components is atleast about 1 or higher. For example, DOS is at least about 1.2, 1.5,1.7, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0. In some embodiments, DOS isbetween about 5.0 to abut 100, between about 100 to 500, or betweenabout 500 to 1,000. It should be noted that DOS can be any number in theabove range. In other embodiments, DOS exceeds 1,000 or even 10,000 to25,000 or 50,000.

In some embodiments the HMW component and the LMW component aredistinct. The term “distinct” as used herein in reference to themolecular weight distribution of the LMW component and the HMW componentmeans the DOS is greater than 1.0 and there is no substantialoverlapping of the two corresponding molecular weight distributions inthe resulting GPC curve. That is, each molecular weight distribution issufficiently narrow and their average molecular weights are sufficientlydifferent that the MWD of both components substantially exhibits abaseline on its high molecular weight side as well as on its lowmolecular weight side.

In some embodiments, even where the HMW component and LMW component havea large DOS or are distinct, the overall MWD of the composition is stillrelatively narrow. In some embodiments, the MWD of the overallcomposition is about 3.0, about 3.5 about 4.0 or about5.0. In otherembodiments the overall MWD may be greater than about 6.0, about 8,about 10, or about 12. Some compositions may have an overall MWD greaterthan about 15 or 20.

One factor that influences the overall MWD is the difference between themolecular weights of the HMW component and the LMW component. In someembodiments, the ratio of the molecular weights of the HMW component andthe LMW component, M_(w) ^(H/M) _(w) ^(L) may be about 1.5, about 2.0,about 3.0 or greaterthan about 4.0, about 6.0, or about 8.0. PreferablyM_(w) ^(H/M) _(w) ^(L) is greater than about 10. Generally, the ratio,M^(H/M) _(w) ^(L), is in the range from about 12 to about 60, preferablyin the range from about 15 to about 40, still more preferably from about15 to about 30, and most preferably from about 15 to about 20. In otherembodiments, the ratio M_(w) ^(H)/M_(w) ^(L) can be greater than 60(e.g., 70, 80, 90, or even 100), but it is generally less preferred.

Another factor that can have a substantial effect on the overall MWD isthe “polymer split” of the composition. A “polymer split” is defined asthe weight fraction of the high molecular weight polymer component in apolymer composition. The relative fraction of the high and low molecularweight components are determined from the deconvoluted GPC peak.Compositions with a split of 1% to 50% are preferred. Some compositionshave a split of about 1.5, about 2.0 or about 2.5 wt. %. Othercompositions have a split of about 3 wt. %, about 5 wt. %, about 10 wt.%, or about 15 wt. %. Still others have a split of about 20 wt. %, about30 wt. %, or about 45 wt. %.

The interpolymers produced in accordance with some embodiments of theinvention have relatively high levels of long chain branches (“LCB”).Long chain branching is formed in the novel interpolymers disclosedherein by reincorporation of vinyl-terminated polymer chains. As such,the distribution of the length of the LCBs correspond to the molecularweight distribution of yinyl-terminated polymer molecules within thepolymer sample. Long-chain branches for the purposes of this inventionrepresent the branches formed by reincorporation of vinyl-terminatedmacromers, not the branches formed by incorporation of the comonomers.The number of carbon atoms on the long chain branches ranges from achain length of at least one carbon more than two carbons less than thetotal number of carbons in the comonomer to several thousands. Forexample, a long chain branch of an ethylene/octene substantially linearethylene interpolymer is at least seven (7) carbons in length (i.e., 8carbons less 2 equals 6 carbons plus one equals seven carbons long chainbranch length). The level of LCBs refers to the number of long chainbranches per 1000 carbon atoms. Typically, the level of LCBs in theinterpolymers is about 0.02 branch/1000 carbons or higher. Someinterpolymers may have about 0.05 to 1 LCB/1000 carbons, or even 0.05 toabout 3 LCBs/1000 carbons, whereas other interpolymers may have about0.1 LCBs/1000 carbons to about 10 LCBs/1000 carbons. Still otherinterpolymers may have LCB exceeding 10/1000 carbons. Preferably, thelevel of long chain branching is 0.05 to about 10, although higherlevels of LCB may have some beneficial effects. For example, an ethyleneinterpolymer with LCBs is observed to possess improved processability,such as shear thinning and delayed melt fracture, as described in U.S.Pat. No.5,272,236. It is expected that a higher level of LCB in aninterpolymer may further improve the processability and melt strength.

For certain of the embodiments of the invention, the polymers can bedescribed as having a “comb-like” LCB structure. For the purposes ofthis invention, a “comb-like” LCB structure refers to the presence ofsignificant levels of polymer molecules having a relatively longbackbone and having a plurality of long chain branches whicharerelatively short compared to the length of the backbone. LCB's thatgenerally are less than about one third of the length of the polymerbackbone on average are considered to be relatively short for thepurposes of this invention. For example, a polymer comprising individualmolecules having a backbone of about 5,000 carbons on average and 3 longchain branches of about 500 carbons each on average would have a“comb-like” structure.

Various methods are known for determining the presence of long chainbranches. For example, long chain branching can be determined for someof the inventive interpolymers disclosed herein by using ¹³C nuclearmagnetic resonance (NMR) spectroscopy and to a limited extent, e.g. forethylene homopolymers and for certain copolymers, and it can bequantified using the method of Randall, (Journal of MacromolecularScience, Rev. Macromol.Chem. Phys. C29 (2&3), p. 285-297). Althoughconventional ¹³C nuclear magnetic resonance spectroscopy cannotdetermine the length of a long chain branch in excess of aboutsix carbonatoms, there are other known techniques useful for quantifying ordetermining the presence of long chain branches in ethylene polymers,such as ethylene/1-octene interpolymers. For those interpolymers whereinthe ¹³C resonances of the comonomer overlap completely with the ¹³Cresonances of the long-chain branches, either the comonomer or the othermonomers (such as ethylene) can be isotopically labeled so that the LCBcan be distinguished from the comonomer. For example, a copolymer ofethylene and 1-octene can be prepared using ¹³C-labeled ethylene. Inthis case, the LCB resonances associated with macromer incorporationwill be significantly enhanced in intensity and will show coupling toneighboring ¹³C carbons, whereas the octene resonances will beunenhanced.

The branching index may also be used to quantify the degree of longchain branching in a selected thermoplastic polymer. The branching indexg′ is defined by the following equation: $\begin{matrix}{{g^{\prime} = \frac{{IV}_{Br}}{{IV}_{Lin}}}}_{M_{w}} & (V)\end{matrix}$where g′ is the branching index, IV_(Br) is the intrinsic viscosity ofthe branched thermoplastic polymer (e.g., polypropylene) and IV_(Lin) isthe intrinsic viscosity of the corresponding linear thermoplasticpolymer having the same weight average molecular weight and molecularweight distribution as the branched thermoplastic polymer and, in thecase of copolymers and terpolymers, substantially the same relativemolecular proportion or proportions of monomer units. For the purposes,the molecular weight and molecular weigh distribution are considered“the same” if the respective values for the branched polymer and thecorresponding linear polymer are within 10% of each other. Preferably,the molecular weights are the same and the MWD of the polymers arewithin 10% of each other. Intrinsic viscosity, in the formula above, inits most general sense is a measure of the capacity of a polymermolecule to enhance the viscosity of a solution. This depends on boththe size and the shape of the dissolved polymer molecule. Hence, incomparing a nonlinear polymer with a linear polymer of substantially thesame weight average molecular weight, it is an indication ofconfiguration of the nonlinear polymer molecule. Indeed, the above ratioof intrinsic viscosities is a measure of the degree of branching of thenonlinear polymer. A method for determining intrinsic viscosity ofpolyethylene is described in Macromolecules, 2000, 33, 7489-7499. Inthis specification the intrinsic viscosityr in each instance isdetermined with the polymer dissolved in decahydronaphthalene at 135° C.Another method for measuring the intrinsic viscosity of a polymer isASTM D5225-98—Standard Test Method for Measuring Solution Viscosity ofPolymers with a Differential Viscometer, which is incorporated byreference herein in its entirety.

The branching index. g′ is inversely proportional to the amount ofbranching. Thus, lower values for g′ indicate relatively higher amountsof branching. The amounts of short and long chain branching eachcontribute to the branching index according to the formula:g=g′_(LCB)×g′_(SCB). Thus, the branching index due to long chainbranching may be calculated from the experinentally determined value forg′ as described by Scholte, et al. in J. App. Polymer Sci., 29,3763-3782 (1984), incorporated herein by reference. Preferably, theweight averaged long chain branching index g′_(LCB) of the compositionis less than about 0.9, 0.8, 0.7, 0.6 or 0.5. In some embodiments, thebranching index is in the range from about 0.01 to about 0.4.

In some embodiments g′_(LCB) is substantially uniform across the polymercomposition. In some embodiments, substantially uniform across thepolymer composition means that the value of g′_(LCB) of the HMWcomponent and the value of g′_(LCB) for the LMW component aresubstantially equal. Alternatively, in someembodiments a substantiallyuniform long chain branching index may also be determined by measuringthe branching index for two different weight fractions of the polymercomposition. In such embodiments, the first weight fraction has amolecular weight, M_(w), of 100,000 andthe second fraction has amolecular weight, M_(w), of 500,000. In the case, the polymer does nothave a significant fraction with M_(w) of 500,000, the branching indexof the fraction may be determined by preparing a polymer using the samecatalysts at conditions that produce a suitable amount of a fractionhaving a M_(w) of 500,000. The long chain branching index of thisfraction is determined and attributed the polymer lacking the 500,000fraction. One skilled in the art knows how increase high molecularweight fractions in a polymerization process. One method for obtainingsuch fractions is by preparative GPC techniques. For the purposes ofbranching indices, the terms “substantially equal” and “substantiallyuniform” mean that the difference between the weight average long chainbranching indices is less than or equal to about 0.22. In someembodiments, the difference in the long chain branching indices is lessthan or equal to about 0.21, about 0.20, about 0.18, or about 0.15. Inother embodiments the difference is less than or equal to about 0.13,about 0.12, about 0.10, about 0.05, or about 0.02.

In some embodiments, high levels of branching in the HMW component maybe desirable. Thus, in some embodiments, the weight average branchingindex g′_(LCB) for the HMW component is less than 0.95, 0.93, or 0.90.In other embodiments the g′_(LCB) for the HMW component, is less than0.88, 0.85 or 0.83. In some embodiments, the LMW component may have ahigh degree of branching. The weight average branching index g′_(LCB)for the LMW component is less than 0.95, 0.93, or 0.90. In otherembodiments the g′_(LCB) for the HMW component, is less than 0.88, 0.85or 0.83.

Two other useful methods for quantifying or determining the presence oflong chain branches in ethylene polymers, such as ethylene/1-octeneinterpolymers, are gel permeation chromatography coupled with a lowangle laser light scattering detector (GPC-LALLS) and GPC-FTIR asdescribed by Rudin, A., Modern Methods of Polymer Characterization, JohnWiley & Sons, New York (1991) pp. 103-112 and Markel, E. J., et al.Macromolecules, 2000, 33,.8541-48 (2000), the disclosures of both ofwhich are incorporated by reference.

Alternatively, the amount of long chain branching in the LMW componentmay be determined by comparing the deconvoluted LMW peak topolymerization models for single-site catalysts. These models arereported by Soares and Hamielec, Macromol. Theory Simul., 5, pp 547-572(1996) and Costeux et al., accepted to Macromolecules (2002),incorporated herein by reference in its entirety. After deconvolution,the number and weight average molecular weights of the LMW component arecalculated and LCBs/1000 carbons can then be determined byLCBs/1000C=(7000/M _(n) ^(L))(M _(n) ^(L) /M _(n) ^(L))−2)  (VI)

The molecular weight averages are determined from GPC with a lightscattering detector to properly account for long chain branching andcomonomer. Since all of the polymer segments under the low molecularweight peak originate from the low molecular weight catalyst, thecomonomer distribution will be constant throughout the low molecularweight peak. Therefore, the presence of comonomer does not complicatethe analysis.

The amount of long chain branching can also be determined by fitting thepredicted molecular weight distribution to the deconvoluted LMW peak.The first step of this approach is to determine the probabilities ofbranching and termination based on input values of the molecular weightof the low molecular weight component, M_(wL) and LCBs/1000 carbons. Theexperimentally determined peak due to the LMW component is compared to asummation of the equation: $\begin{matrix}{{w(M)} = {\sum\limits_{y}{w\left( {M,y} \right)}}} & ({VII})\end{matrix}$over a range of branch contents, y.

Adjusting the value of M_(n) ^(L) will shift the predicted molecularweight distribution so that its peak will occur at the same molecularweight as the experimental data's peak. For low molecular weightcatalysts that incorporate long chain branches, the width of thepredicted molecular weight distribution will only match the breadth ofthe experimental peak if the input LCBs/1000 carbons is greater thanzero.

In some embodiments, polymers having relatively high melt strength havea relatively higher degree of long chain branching in the high molecularweight component. For instance, some polymers have a high molecularweight component that has an average of greater than about 2 branchesper polymer chain. Other embodiments may have an average of greater thanabout 3, about 4, or about 5 branches per chain in the high molecularweight fraction. Still other polymers may have a high molecular weightcomponent with an average of greater than about 6, about 8, or about 10branches. In some embodiments, the number of branches on the highmolecular weight component may be even higher.

The formation of long chain branching depends on a number of factors,including but not limited to, monomer (or comonomer) concentration,reactor temperature, pressure, polymer concentration, and catalyst(s)used. Generally, a higher level of long chain branching may be obtainedwhen a polymerization reaction is operated at a higher temperature, alower comonomer concentration, a higher polymer concentration, and usingcatalysts which can generate a relatively high percentage of vinyl endgroups and have relatively high comonomer incorporation ability (i.e.,lower r₁). Conversely, a lower level of long chain branching may beobtained when a polymerization reaction is operated at a lowertemperature, a higher comonomer concentration, a lower polymerconcentration, and using catalysts which can generate a relatively lowpercentage of vinyl end groups and have relatively low comonomerincorporation ability (i.e., higher r₁).

The polymer composition may be made by a variety of methods. Tailoredpolymers with desirable properties can be prepared by controlling thedistribution and nature of long-chain branching between the highmolecular weight component(s) and the low molecular weight component(s)of the polymer produced using more than one catalyst in the novelprocess described herein. For example, a suitable process comprises: (a)contacting one or more olefinic monomers in the presence of at least ahigh molecular weight (HMW) catalyst and at least a low molecular weight(LMW) catalyst in a polymerization reactor system and (b) effectuatingthe polymerization of the one or more olefinic monomers in thepolymerization reactor system to obtain an olefin polymer, wherein theLMW catalyst has an R_(v), defined as $\begin{matrix}{R_{v} = \frac{\text{[vinyl]}}{\text{[vinyl]} + \text{[vinylidene]} + \text{[cis]} + \text{[trans]}}} & ({VIII})\end{matrix}$wherein [vinyl] is the concentration of vinyl groups in the olefinpolymer produced by the low molecular weight catalyst expressed invinyls/1,000 carbon atoms; [vinylidene], [cis] and [trans] are theconcentration of vinylidene, cis and trans groups in the olefin polymerexpressed in the number of the respective groups per 1,000 carbon atoms,of greater than 0.12, and wherein the HMW catalyst has a reactivityratio, r₁ of about 5 or less. Preferably, the high molecular weightcatalyst and the low molecular weight catalyst have the ability toincorporate a substantially similar amount of comonomers.

The process described herein may be employed to prepare any olefinpolymers, including but not limited to, ethylene/propylene,ethylene/1-butene, ethylene/1-hexene, ethylene/4-methyl-1-pentene,ethylene/styrene, ethylene/propylene/styrene, and ethylene/1-octenecopolymers, isotactic polypropylene/1-butene, isotacticpolypropylene/1-hexene, isotactic polypropylene/1-octene, terpolymers ofethylene, propylene and a non-conjugated diene, i.e., EPDM terpolymers,as well as homopolymers of ethylene, propylene, butylene, styrene, etc.

Olefins as used herein refer to a family of unsaturatedhydrocarbon-based compounds with at least one carbon-carbon double bond.Depending on the selection of catalysts, any olefin may be used inembodiments of the invention. Preferably, suitable olefins are C₂₋₂₀aliphatic and aromatic compounds containing vinylic unsaturation, aswell as cyclic compounds, such as cyclobutene, cyclopentene,dicyclopentadiene, and norbornene, including but not limited to,norbomene substituted in the 5 and 6 position with C₁₋₂₀ hydrocarbyl orcyclohydrocarbyl groups. Also included are mixtures of such olefins aswell as mixtures of such olefins with C₄₋₄₀ diolefin compounds.

Examples of olefin monomers include, but are not limited to ethylene,propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, and 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene,3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene,4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidenenorbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene,C₄₋₄₀ dienes, including but not limited to 1,3-butadiene,1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene,1,9-decadiene, other C₄₋₄₀ α-olefns, and the like. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedrnonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The novel processes described herein are well suited for the productionof olefm polymers comprising monovinylidene aromatic monomers includingstyrene, o-methyl styrene, p-methyl styrene, t-butylstyrene, and thelike. In particular, interpolymers comprising ethylene and styrene canbe advantageously prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃₋₂₀ alphaolefin, optionally comprising a C₄₋₂₀ diene, having improved propertiesover those presently known in the art can be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2, 5-diene; alkenyl,aLkylidene, cycloalkenyl and cycloalkylidene norbomenes, such as5-methylene-2-norbornene (MNB);5-propenyl-2-norbomene,5-isopropylidene-2-norbomene,5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene,5-vinyl-2-norbornene, and norbomadiene. Of the dienes typically used toprepare EPDMs, the particularly preferred dienes are 1,4-hexadiene (HD),5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB),5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD). Theespecially preferred dienes are 5-ethylidene-2-norbomene (NB) and1,4-hexadiene (HD).

In the process, a high molecular weight catalyst is defined relative toa low molecular weight catalyst. A high weight molecular weight catalystrefers to a catalyst which produces a polymer with a high weight-averagemolecular weight M_(w) ^(H) from the monomers and any comonomers ofchoice under a set of given polymerization conditions, whereas a lowmolecular weight catalyst refers to a catalyst which produces a polymerwith a low weight average molecular weight M_(wL) from the same monomersand comonomers under substantially the same polymerization conditions.Therefore, the terms “low molecular weight catalyst” and “high molecularweight catalyst” used herein do not refer to the molecular weight of acatalyst; rather, they refer to a catalyst's ability to make a polymerwith alow or high molecular weight. The intrinsic molecular weightdifferences in the polymer produced by the chosen high and low molecularweight catalysts produces “polymer split” of the composition.

Thus, a high molecular weight catalyst and a low molecular weightcatalyst are determined with reference to each other. One does not knowwhether a catalyst is a high molecular weight catalyst or a lowmolecular weight catalyst until after another catalyst is also selected.Therefore, the terms “high molecular weight” and “low rmolecular weight”used herein when referring to a catalyst are merely relative terms anddo not encompass any absolute value with respect to the molecular weightof a polymer. After a pair of catalysts selected, one can easilyascertain which one is the high molecular weight catalyst by thefollowing procedure: 1) select at least one monomer which can bepolymerized by the chosen catalysts; 2) make a polymer from the selectedmonomer(s) in a single reactor containing one of the selected catalystsunder pre-selected polymerization conditions; 3) make another polymerfrom the same monomer(s) in a single reactor containing the othercatalyst under substantially the same polymerization conditions; and 4)measure the melt index I₂ for the respective interpolymers. The catalystthat yields a lower I₂ is the higher molecular weight catalyst.Conversely, the catalyst that yields a high I₂ is the lower molecularweight catalyst. Using this methodology, it is possible to rank aplurality of catalysts based on the molecular weight of the polymersthey can produce under substantially the same conditions. As such, onemay select three, four, five, six, or more catalysts according theirmolecular weight capability and use these catalysts simultaneously in asingle. polymerization. reactor to produce polymers with tailoredstructures and properties.

In some embodiments, the high molecular weight catalysts and the lowmolecular weight catalysts are selected such that they have the abilityto incorporate a substantially similar amount of comonomers in thepolymer. In other words, under substantially the same conditions oftemperature, pressure, and monomer content (including comonomerconcentration), each catalyst incorporates substantially the same molepercentage of comonomers into the resulting interpolymer. One way toquantify “substantially the same” or “substantially similar” molepercentage of comonomers is as follows: where a first catalystincorporatesless than 5mole % of comonomers under a set ofpolymerization conditions, a second catalyst incorporates the same molepercentage of comonomers within 2 mole %. For example, if the firstcatalyst incorporates 4 mole % 1-octene in an ethylene-1-octenecopolymerization, then the second catalyst would exhibit substantiallythe same comonomer incorporation if it yields an interpolymer with about2.0 mole % to about 6.0 mole % octene under substantially the samepolymerization conditions of temperature, pressure, comonomerconcentration, and comonomer type. For a catalyst with about 5 mole % toabout 10 mole % comonomer incorporation, the range for “substantiallythe same comonomer incorporation” for a second catalyst is within 3 mole% of the comonomer incorporation For a catalyst with about 10 mole % toabout 20 mole %, the range for “substantially the same comonomerincorporation” would be within 4 mole %. For a catalyst whichincorporates 20 mole % or higher comonomers, the range for“substantially the same comonomer incorporation” for another catalystwould be within 6 mole %.

For the case of an olefin homopolymer, two catalysts are considered tohave “substantially the same comonomer incorporation” if the twocatalysts, under reaction conditions equivalent to the conditions usedto make a homopolymer but differing in that if 1-octene is used as acomonomer in an amount such that one of the catalysts produces a 1.0mole % octene copolymer, the other catalyst produces a 1-octenecopolymer with the same mole % octene within 0.75 mole %. For thespecial case of a 1-octene homopolymer, 1-decene is used as thecomonomer.

Preferably, for all of the ethylene homopolymers and interpolymersdescribed immediately above, at least two of the catalysts used in asingle reactor have substantially the .same comonomer incorporation, andthe process used is a gas phase, slurry, or solution process. Morepreferably, for all of the ethylene homopolymers and interpolymersdescribed immediately above, at least two of the catalysts used in asingle reactor have substantially the same comonomer incorporation,M_(w) ^(H/M) _(w) ^(L) is in the range from about 10 to about 50, andthe process used is a continuous solution process, especially acontinuous solution process wherein the polymer concentration in thereactor at steady state is at least 15% by weight of the reactorcontents and the ethylene concentration is 3.5% or less by weight of thereactor contents. Still more preferably, the process used is acontinuous solution process wherein the polymer concentration in thereactor at steady state is at least 18% by weight of the reactorcontents and the ethylene concentration is 2.5% or less by weight of thereactor contents. Most preferably, for all of the ethylene homopolymersand interpolymers described immediately above, at least two of thecatalysts used in a single reactor have substantially the same comonomerincorporation, and the process used is a continuous solution processwherein the polymer concentration in the reactor at steady state is atleast 20% by weight of the reactor contents and the ethyleneconcentration is 2.0% or less by weight of the reactor contents. For allof the ethylene homopolymers and interpolymers described immediatelyabove, preferably the interpolymers comprise an interpolymer of ethyleneand at least one olefin selected from the group consisting of C₃-C₁₀alpha olefins, especially propylene, 1-butene, 1-hexene, and 1-octene,and the melt index of the interpolymer is preferably in the range ofabout 0.1 to about 500, more preferably in the range from about 0.1 toabout 100.

Comonomer incorporation can be measured by many techniques that areknown in the art. One technique which may be employed is ¹³C NMRspectroscopy, an example of which is described for the determination ofcomonomer content for ethylene/alpha-olefin copolymers in Randall(Journal of Macromolecular Science, Reviews in Macromolecular Chemistryand Physics, C29 (2 & 3), 201-317 (1989)), the disclosure of which isincorporated herein by reference. The basic procedure for determiningthe comonomer content of an olefin interpolymer involves obtaining the¹³C NMR spectrum under conditions where the intensity of the peakscorresponding to the different carbons in the sample is directlyproportional to the total number of contributing nuclei in the sample.Methods for ensuring this proportionality are known in the art andinvolve allowance for sufficient time for relaxation after a pulse, theuse of gated-decoupling techniques, relaxation agents, and the like. Therelative intensity of a peak or group of peaks is obtained in practicefrom its computer-generated integral. After obtaining the spectrum andintegrating the peaks, those peaks associated with the comonomer areassigned. This assignment can be made by reference to known spectra orliterature, or by synthesis and analysis of model compounds, or by theuse of isotopically labeled comonomer. The mole % comonomer can bedetermined by the ratio of the integrals corresponding to the number ofmoles of comonomer to the integrals corresponding to the number of molesof all of the monomers in the interpolymer, as described in Randall, forexample.

It is known in the art that catalysts for olefin polymerization canchange in their ability to incorporate comonomers under differentreaction conditions, especially at different reactor temperatures. Forexample, it is known that the ability of most single-site andmetallocene catalysts to incorporate higher alpha olefins in anethylene/alpha olefin, copolymerization decreases with increasingpolymerization temperature. In other words, the reactivity ratio rigenerally increases with increasing polymerization temperature.

The reactivity ratios of the metallocenes in general are obtained byknown methods, for example, as described in “Linear Method forDetermining Monomer Reactivity Ratios in Copolymerization”, M. Finemanand S. D. Ross, J. Polymer Science 5, 259 (1950) or “Copolymerization”,F. R. Mayo and C. Walling, Chem. Rev. 46, 191 (1950) incorporated hereinin its entirety by reference. For example, to determine reactivityratios the most widely used copolymerization model is based on thefollowing equations:

where M_(i) refersto a monomer molecule which is arbitrarily designatedas “i” where i=1, 2; and M₂* refers to a growing polymer chain to whichmonomer i has most recently attached.

The k_(ij) values are the rate constants for the indicated reactions.For example, in ethylene/propylene copolymerization, k₁₁ represents therate at which an ethylene unit inserts into a growing polymer chain inwhich the previously inserted monomer unit was also ethylene. Thereactivity ratios follow as: r₁=k₁₁/k₁₂ and r₂=k₂₂/k₂₁ wherein k₁₁, k₁₂,k₂₂ and k₂₁ are the rate constants for ethylene (1) or propylene (2)addition to a catalyst site where the last polymerized monomer is anethylene (k_(1x)) or propylene (k_(2x)).

Because the change in r₁ with temperature may vary from catalyst tocatalyst, it should be appreciated that the term “substantially the samecomonomer incorporation” refers to catalysts which are compared at thesame or substantially the same polymerization conditions, especiallywith regard to polymeriization temperature. Thus, a pair of catalystsmay not possess “substantially the same comonomer incorporation” at alow polymerization temperature, but may possess “substantially the samecomonomer incorporation” at a higher temperature, and visa versa. Forthe purposes of this invention, “substantially the same comonomerincorporation” refers to catalysts which are compared at the same orsubstantially the same polymerization temperature. Because it is alsoknown that different cocatalysts or activators can have an effect on theamount of comonomer incorporation in an olefin copolymerization, itshould be appreciated that “substantially the same comonomerincorporation” refers to catalysts which are compared using the same orsubstantially the same cocatalyst(s) or activator(s). Thus, for thepurposes of this invention, a test to determine whether or not two ormore catalysts have “substantially the same comonomer incorporation”should be conducted with each catalyst using the same method ofactivation for each catalyst, and the test should be conducted at thesame polymerization temperature, pressure, and monomer content(including comonomer concentration) as is used in the instant inventiveprocess when the individual catalysts are used together.

When a low molecular weight catalyst with r₁ ^(L) and a high molecularweight catalyst with r₁ ^(H) are selected, the r₁ ratio, r_(l) ^(H)/r₁^(L), is another way to define the amount of comonomer incorporation bythe low and high molecular weight catalysts. To have substantiallysimilar or the same comonomer incorporation in some embodiments of theinvention, the ratio, r₁ ^(H)/r₁ _(L), preferably should fall betweenabout 0.2 to about 5, more preferably between about 0.25 to about 4, andmost preferably between about 0.3 to about 3.5. In some embodiments,substantially similar or the same comonomer incorporation is obtainedwhen the ratio, r₁ ^(H)/r₁ ^(L), approaches about 1 (i.e., from about0.9 to about 1.1).

Although r₁ may be any value, it preferably should be about 18 or less.For example, r₁ may be about 15, 10, 5, or 1. Generally, a lower r₁indicates a higher comonomer incorporation ability for the catalyst.Conversely, a higher r₁ generally indicates a lower comonomerincorporation ability for the catalyst (i.e., a higher tendency to makea homopolymer). Therefore, if one desires to make a copolymer with aminimal density split, it would be preferable to use at least twocatalysts with substantially similar or identical r₁, each of which isless than 18. On the other hand, when one desires to make a blend ofhomopolymers and copolymers with a significant density split, it wouldbe preferable to employ at least two catalysts with substantiallydissimilar r₁, at least one of which may be higher than 18.

As described above, while it is preferred to select a high molecularweight catalyst and a lower molecular weight catalyst with substantiallysimilar comonomer incorporation capability, catalysts with different orsubstantially dissimilar comonomer incorporation capability may be usedin embodiments of the invention. When two catalysts have substantiallysimilar comonomer incorporation capability, the interpolymer producedhas a minimal density split, i.e., minimal density variations from onepolymer chain to another. In contrast, when two catalysts have differentor substantially dissimilar comonomer incorporation capability, theinterpolymer produced by those two catalysts has a substantial densitysplit. Such density split has a direct impact on the physicalcharacteristics of the interpolymer. Generally, for many applications itis more desirable to produce an interpolymer with a minimal densitysplit.

Catalysts:

Any catalyst which is capable of copolymerizing one or more olefinmonomers to make an interpolymer or homopolymer may be used inembodiments of the invention. For certain embodiments, additionalselection criteria, such as molecular weight capability and/or comonomerincorporation capability, preferably should be satisfied. Suitablecatalysts include, but are not limited to, single-site catalysts (bothmetallocene catalysts and constrained geometry catalysts), multi-sitecatalysts (Ziegler-Natta catalysts), and variations therefrom. Theyinclude any known and presently unknown catalysts for olefinpolymerization. It should be understood that the term “catalyst” as usedherein refers to a metal-containing compound which is used, along withan activating cocatalyst, to form a catalyst system. The catalyst, asused herein, is usually catalytically inactive in the absence of acocatalyst or other activating technique. However, not all suitablecatalyst are catalytically inactive without a cocatalyst and thusrequires activation.

One suitable class of catalysts is the constrained geometry catalystsdisclosed in U.S. Pat. No. 5,064,802, No. 5,132,380, No. 5,703,187, No.6,034,021, EP 0 468 651, EP 0 514 828, WO 93/19104, and WO 95/00526, allof which are incorporated by references herein in their entirety.Another suitable class of catalysts is the metallocene catalystsdisclosed in U.S. Pat. No. 5,044,438; No. 5,057,475; No. 5,096,867; andNo. 5,324,800, all of which, are incorporated by reference herein intheir entirety. It is noted that constrained geometry catalysts may beconsidered as metallocene catalysts, and both are sometimes referred toin the art as single-site catalysts.

For example, catalysts may be selected from the metal coordinationcomplexes corresponding to the formula:

wherein: M is a metal of group 3, 4-10, or the lanthanide series of theperiodic table of the elements; Cp* is a cyclopentadienyl or substitutedcyclopentadienyl group bound in an η⁵ bonding mode to M; Z is a moietycomprising boron, or a member of group 14 of the periodic table of theelements, and optionally sulfur or oxygen, the moiety having up to 40non-hydrogen atoms, and optionally Cp* and Z together form a fused ringsystem; X independently each occurrence is an anionic ligand group ,said X having up to 30 non-hydrogen atoms; n is 2 less than the valenceof M when Y is anionic, or 1 less than the valence of M when Y isneutral; L independently each occurrence is a neutral Lewis base ligandgroup, said L having up to 30 non-hydrogen atoms; m is 0, 1, 2, 3, or 4;and Y is an anionic or neutral ligand group bonded to Z and M comprisingnitrogen, phosphorus, oxygen or sulfur and having up to 40 non-hydrogenatoms, optionally Y and Z together form a fused ring system.

Suitable catalysts may also be selected from the metal coordinationcomplex corresponds to the formula:

wherein R′ each occurrence is independently selected from the groupconsisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo andcombinations thereof having up to 20 non-hydrogen .atoms; X.eachoccurrence independently. is selected from the group consisting ofhydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide,siloxy, and combinations thereof having up to 20 non-hydrogen atoms; Lindependently each occurrence is a neural Lewis base ligand having up to30 non-hydrogen, atoms; Y is O, —S—, —NR*—, —PR*—, or a neutral twoelectron donor ligand selected from the group consisting of OR*, SR*,NR*₂, PR*₂; M, n, and m are as previously defined; and Z is SIR*₂, CR*₂,SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂, GeR*₂, BR*, BR*₂; wherein: R*each occurrence is independently selected from the group consisting ofhydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groupshaving up to 20 non-hydrogen atoms, and mixtures thereof, or two or moreR* groups from Y, Z, or both Y and Z form a fused ring system.

It should be noted that whereas formula I and the following formulasindicate a monomeric structure for the catalysts, the complex may existas a dimer or higher oligomer.

Further preferably, at least one of R′, Z, or R* is an electron donatingmoiety. Thus, highly preferably Y is a nitrogen or phosphorus containinggroup corresponding to the formula —N(R″″ or —P(R″″)—, wherein R″″ isC₁₋₁₀ alkyl or aryl, i.e., an amido or phosphido group.

Additional catalysts may be selected from the amidosilane- oramidoalkanediyl-compounds corresponding to the formula:

wherein: M is titanium, zirconium or hafnium, bound in an η⁵ bondingmode to the cyclopentadienyl group; R′ each occurrence is independentlyselected from the group consisting of hydrogen, silyl, alkyl, aryl andcombinations thereof having up to 10 carbon or silicon atoms; E issilicon or carbon; X independently each occurrence is hydride, halo,alkyl, aryl, aryloxy or alkoxy of up to 10 carbons; m is 1 or 2; and nis 1 or 2 depending on the valence of M.

Examples of the above metal coordination compounds include, but arenotlimited to, compounds in which the R′ on the amido group is methyl,ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbomnyl,benzyl, phenyl, etc.; the cyclopentadienyl group is cyclopentadienyl,indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, etc.; R′ onthe foregoing cyclopentadienyl groups each occurrence is hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers),norbomyl, benzyl, phenyl, etc.; and X is chloro, bromo, iodo, methyl,ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl,benzyl, phenyl, etc.

Specific compounds include, but are not limited to,(tertbutylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconiumdimethyl, (tert-butylamido) (tetramethyl-η⁵-cyclo pentadienyl)-1,2-ethanediyltitanium dimethyl, (methylamido)(tetrrrethyl-η⁵-cyclopenta dienyl)-1,2-ethanediyizirconium dichloride,(methylamido)(tetramethyl-η⁵-eyelopenta dienyl)-1,2-ethane diyltitaniumdichloride,(ethylamido)(tetramethyl-η⁵-cyclopentadienyl)-methylenetitaniumdichloro,(tertbutylamido)diphenyl(tetramethyl-η⁵-cyclopentadienyl)-silanezirconium dibenzyl,(benzylamido)dimethyl-(tetramethyl-η⁵-cyclopentadienyl)ilanetitaniumdichloride,phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl) silanezirconium dibenzyl, and the like.

Another suitable class of catalysts is substituted indenyl containingmetal complexes as disclosed in U.S. Pat. No. 5,965,756 and No.6,015,868 which are incorporated by reference herein in their entirety.Other catalysts are disclosed in copending applications: U.S.application Ser. No. 09/230,185; and No. 09/715,380, and U.S.Provisional Application Ser. No. 60/215,456; No. 60/170,175, and No.60/393,862. The disclosures of all of the preceding patent applicationsare incorporated by reference herein in their entirety. These catalyststend to have a. higher molecular weight capability.

One class of the above catalysts is the indenyl containing metalwherein:

-   -   M is titanium, zirconium or hafnium in the +2, +3 or +4 formal        oxidation state;    -   A′ is a substituted indenyl group substituted in at least the 2        or 3 position with a group selected from hydrocarbyl,        fluoro-substituted hydrocarbyl, hydrocarbyloxy-substituted        hydrocarbyl, dialkylamino- substituted hydrocarbyl, silyl,        germyl and mixtures thereof, the group containing up to 40        non-hydrogen atoms, and the A′ further being covalently bonded        to M by means of a divalent Z group; Z is a divalent moiety        bound to both A′ and M via σ-bonds, the Z comprising boron, or a        member of Group 14 of the Periodic Table of the Elements, and        also comprising nitrogen, phosphorus, sulfur or oxygen; X is an        anionic or dianionic ligand group having up to 60 atoms        exclusive of the class of ligands that are cyclic, delocalized,        π-bound ligand groups; X′ independently each occurrence is a        neutral Lewis base, having up to 20 atoms; p is 0, 1 or 2, and        is two less than the formal oxidation state of M, with the        proviso that when X is a dianionic ligand group, p is 1; and q        is 0, 1 or 2.

The above complexes may exist as isolated crystals optionally in pureform or as a mixture with other complexes, in the form of a solvatedadduct, optionally in a solvent, especially an organic liquid, as wellas in the form of a dimer or chelated derivative thereof, wherein thechelating agent is an organic material, preferably a neutral Lewis base,especially a trihydrocarbylamine, trihydrocarbylphosphine, orhalogenated derivative thereof.

Preferred catalysts are complexes corresponding to the formula:

wherein R₁ and R₂ independently are groups selected from hydrogen,hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germyl andmixtures thereof, the group containing up to 20 non-hydrogen atoms, withthe proviso that at least one of R₁ or R₂ is not hydrogen; R₃, R₄, R₅,and R₆ independently are groups selected from hydrogen, hydrocarbyl,perfluoro substituted hydrocarbyl, silyl, germyl and mixtures thereof,the group containing up to 20 non-hydrogen atoms; M is titanium,zirconium or hafnium; Z is a divalent moiety comprising boron, or amember of Group 14 of the Periodic Table of the Elements, and alsocomprising nitrogen, phosphorus, sulfur or oxygen, the moiety having upto 60 non-hydrogen atoms; p is 0, 1 or 2; q is zero or one; with theproviso that: when p is 2, q is zero, M is in the +4 formal oxidationstate, and X is an anionic ligand selected from the group consisting ofhalide, hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido,di(hydrocarbyl)phosphido, hydrocarbyl sulfido, and silyl groups, as wellas halo-, di(hydrocarbyl)amino-, hydrocarbyloxy- anddi(hydrocarbyl)phosphino-substituted derivatives thereof, the X grouphaving up to 20 non-hydrogen atoms, when p is 1, q is zero, M is in the+3 formal oxidation state, and X is a stabilizing anionic ligand groupselected from the group consisting of allyl,2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethyl)-aminobenzyl, orM is in the +4 formal oxidation state, and X is a divalent derivative ofa conjugated diene, M and X together forming a metallocyclopentenegroup, and when p is 0, q is 1, M is in the +2 formal oxidation state,and X′ is a neutral, conjugated or non-conjugated diene, optionallysubstituted with one or more hydrocarbyl groups, the X′ having up to 40carbon atoms and forming a π-complex with M.

More preferred catalysts are complexes corresponding to the formula:

wherein: R₁ and R₂ are hydrogen or C₁₋₆ alkyl, with the proviso that atleast one of R₁ or R₂ is not hydrogen; R₃, R₄, R₅, and R₆ independentlyare hydrogen or C₁₋₆ alkyl; M is titanium; Y is —O—, —S—, —NR*—, —PR*—;Z* is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂, or GeR*₂;R* each occurrence is independently hydrogen, or a member selected fromhydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl,and combinations thereof, the R* having up to 20 non-hydrogen atoms, andoptionally, two R* groups from Z (when R* is not hydrogen), or an R*group from Z and an R* group from Y form a ring system; p is 0, 1 or 2;q is zero or one; with the proviso that: when p is 2, q is zero, M is inthe +4 formal oxidation state, and X is independently each occurrencemethyl or benzyl, when p is 1, q is zero, M is in the +3 formaloxidation state, and X is 2-(N,N-dimethyl)aminobenzyl; or M is in the +4formal oxidation state and X is 1,4-butadienyl, and when p is 0, q is 1,M is in the +2 formal oxidation state, and X is1,4-diphenyl-1,3-butadiene or 1,3-pentadiene. The latter diene isillustrative of unsymmetrical diene groups that result in production ofmetal complexes that are actually mixtures of the respective geometricalisomers.

Examples of specific catalysts that may be used in embodiments of theinvention include, but are not limited, the following metal complexes:

2-methylindenyl Complexes:

(t-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (II)1,4diphenyl-1,3-butadiene; (t-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (II) 1,3-pentadiene;(t-butylamido) dimethyl(η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (t-butylamido) dimethyl(η⁵-2-methylindenyl)silanetitanium (IV) dimethyl;(t-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (IV) dibenzyl;(n-butylamido)dimethyl(η⁵-2-methylindenyl) silanetitanium (II)1,4diphenyl- 1,3-butadiene; (n-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (II) 1,3-pentadiene,(n-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl;(n-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (IV) dimethyl;(n-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (IV) dibenzyl;(cyclododecylamido) dimethyl(η⁵-2-methylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene; (cyclododecylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (II) 1,3-pentadiene,(cyclododecylamido)diinethyl(η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (cyclododecylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (IV) dimethyl;(cyclododecylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (IV)dibenzyl; (2,4,6-trimethylanilido)dimethyl(η⁵-2-methylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene;trimethylanilido)dimethyl(η⁵-2-methyl indenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido)dimethyl(η⁵-2-methylindenyl)silanetitanium (IV)dimethyl; (2,4,6-trimethylanilido)dimethyl(η⁵-2-methylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylarnido)dimethyl(η⁵-2-methylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene;(1-adamantylamido)dimethyl(η⁵-2-methylindenyl) silanetitanium (II)1,3-pentadiene;(1-adamantylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl;(1-adamantylamido)dimethyl(η⁵-2-methylindenyl)silane titanium (IV)dimethyl; (1-adamantylarnido)dimethyl(η⁵-2-methylindenyl)silanetitanium(IV) dibenzyl; (t-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(t-butylamido)dimethyl(η-2-methylindenyl)silanetitanium (II)1,3-pentadiene; (t-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (t-butylamido)dimethyl(η⁵-2-methylindenyl)silanetitanium (IV) dimethyl;(t-butylamido)dimethyl(η⁵-2-methyl indenyl)silanetitanium (IV) dibenzyl;(n-butylamido)diisopropoxy(η⁵-2-methylindenyl) silane titanium (II)1,4-diphenyl- 1,3-butadiene;(n-butylamido)diisopropoxy(η⁵-2-methylindenyl) silanetitanium (II)1,3-pentadiene; (n-butylamido)diisopropoxy(η⁵-2-methylindenyl)silanetitanium (III) 2-N,N-dimethylamino)benzyl;(n-butylamido)diisopropoxy(η⁵-2-methylindenyl) silanetitanium (IV)dimethyl; (n-butylamido)diisopropoxy(η⁵-2-methylindenyl) silanetitanium(IV) dibenzyl;(cyclododecylamido)diisopropoxy(η⁵-2-methylindenyl)-silanetitaniuri (II)1,4-diphenyl-1,3-butadiene; (cyclododecylamido)diisoproppxy(η⁵-2-methylindenyl)-silanetitanium (II) 1,3-pentadiene;(cyclododecylamido)diisopropoxy(η⁵-2-methyl indenyl)-silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (cyclododecylamido)diisopropoxy(η⁵-2-methylindenyl)-silanetitanium (IV) dimethyl;(cyclododecylamido)diisopropoxy(η⁵-2-methylindenyl)-silanetitanium (IV)dibenzyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2-methyl-indenyl)silanetitanium(II) 1,4diphenyl-1,3-butadiene;(2,4,6triethylanilido)diisopropoxy(η⁵-2-methylindenyl)silanetitanium(II) 1,3-pentadiene;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2-methylin-denyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (2,4,6-trimethylanilido)diisopropoxy(1⁵-2-methylindenyl)silanetitanium (IV) dimethyl;(2,4,6-trimethylanilido) diisopropoxy(η⁵-2-methylindenyl)silanetitanium(IV) dibenzyl; (1-adamantylamido)diisopropoxy(η⁵-2-methylindenyl)silanetitanium(I),1,4-diphenyl-1,3-butadiene;(1-adamantylamido)diisopropoxy(η⁵-2-methylin4enyl)silanetitanium (II)1,3-pentadiene;(1-adamantylamido)diisopropoxy(η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl;(1-adamantylamido)diisopropoxy(η⁵-2-methylindenyl)silanetitanium (IV)dimethyl;(1-adamantylamido)diisopropoxy(,n⁵-2-methylindenyl)silanetitanium (IV)dibenzyl; (n-butylamido) dimethoxy(η⁵-2-methylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (n-butylamido)dimethoxy(η⁵-2-methylindenyl)silanetitanium (II) 1,3-pentadiene;(n-butylamido) dimethoxy (η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylarnino)benzyl; (n-butylamido) dimethoxy(z⁵-2-methylijidenyl)silanetitanium (IV) dimethyl;(n-butylamido)dimethoxy(η⁵-2-methylindenyl)silanetitanium (IV) dibenzyl;(cyclododecylamido)dinethoxy(η⁵-2-methyl indenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene; (cyclododecylamido)dimethoxy (η⁵-2-methylindenyl)silanetitanium (II) 1,3-pentadiene;(cyclododecylamido)dimethoxy(η⁵-2-methylindenyl) silanetitanium (III)2-(N,N-dimethylamino)benzyl; (cyclododecylamido) dimethoxy(η⁵-2-methylindenyl)silanetitanium (IV) dimethyl; (cyclododecylamido)dimethoxy(η⁵-2-methylindenyl) silanetitanium (IV) dibenzyl;(2,4,6-trimethylanilido)dimethoxy (η⁵-2-methylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)dimethoxy(η⁵-2-methylindenyl) silanetitanium (II) 1,3-pentadiene;(2,4,6-trimethylanilido) dimethoxy(η⁵-2-methylindenyl) silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido)dimethoxy(η⁵-2-methyl indenyl)silanetitanium(IV) dimethyl; (2,4,6-trimethylanilido)dimethoxy(,1⁵-2-methylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)dimethoxy(η⁵-2-methylindenyl)silanetitanium (II).1,4-diphenyl-1,3-butadiene;(1-adamantylamido)dimethoxy(η⁵-2-methylindenyl)silanetitanium (II)1,3-pentadiene;(1-adamantylamido)dimethoxy(η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl;(1-adamantylamido)dimethoxy(η⁵-2-methylindenyl)silanetitanium (IV)dimnethyl; (1-adamantylamido)dimethoxy(η⁵-2-methylindenyl)silanetitanium(IV) dibenzyl;(n-butylamido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(n-butylamido)ethoxymethyl(η5-2-methylindenyl)silanetitanium (II)1,3-pentadiene; (n-butylamido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl; (n-butylamido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (IV) dimethyl;(n-butylamido) ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (IV)dibenzyl; (cyclododecyl amido) ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene;(cyclododecyl amido)ethoxymethyl(η⁵-2-methylindenyl)silanetitani (II)1,3-pentadiene; (cycododecylamido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl; (cyclododecylamido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (IV) dimethyl;(cyclododecylamido) ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (IV)dibenzyl; (2,4,6-trimethylanilido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (II)1,3-pentadiene;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium(III) 2-(N,N-dimethylamino) benzyl;(2,4,6-trimethylanilido)ethoxymethyl(η5-2-methylindenyl) silanetitanium(IV) dimethyl; (2,4,6-trimethylanilido)ethoxymethyl(η⁵ -2-methylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)ethoxymethyl(η5-2-methylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene; (1-adamantylamido)ethoxymethyl(η⁵ -2-methylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylarnido)ethoxymethyl(η⁵-2methyl indenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl; (1-adamantylamido)ethoxymethyl(η⁵-2-methylindenyl)silanetitanium (IV) dimethyl;(1-adamantylamido)ethoxymethyl(η5-2-methylindenyl)silanetitanium (IV)dibenzyl;

2,3-dimethylindenyl Complexes:(t-butylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(t-butylamido)dimethyl(,⁵-2,3-dinethylindenyl)silanetitanium (II)1,3-pentadiene;(t-butylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl;(t-butylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (IV)dimethyl; (t-butyl amido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium(IV) dibenzyl; (n-butylamido)dimethyl(η⁵-2,3-dimethylindenyl)-silanetitanium (II)1,4-diphenyl-1,3-butadiene; (n-butylamido)dimethyl(η⁵-2,3-dinethyhindenyl)silanetitanium (II)1,3-pentadiene; (n-butylamido)diinethyl(η⁵-2,3-dimethylindenyl)-silanetitanium (III)2-(N,N-dimethylamino)benzyl; (n-butylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dimethyl;(n-butylanmido) dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl; (cyclododecylamido) dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (II)1,3-pentadiene; (cyclododecylamido)dimethyl(η⁵-2,3-dimiethylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl; (cyclododecylamido) dimethy(η⁵-2,3-dimethylindenyl) silahetitanium (IV) dimethyl;(cyclododecylamido)dimethyl (η⁵-2,3-dimethylindenyl) silanetitanium (IV)dibenzyl; (2,4,6-trimethylanilido)dimethy (η⁵-2,3-dimethyl-indenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene;(2,4,6-trimethylanilido) dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido)dimethyl(η⁵-2,3-dimethylindenyl) silanetitanium(IV) dimethyl; (2,4,6-tri methylanilido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl; (1-adamantylamido)dimethyl(η⁵-2,3-dimethylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene; (1-adamantylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylamido)dimethyl(η⁵-2,3-dimethyl indenyl)silanetitanium (I)2-(N,N-dimethylamino) benzyl;(1-adamantylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (IV)dimethyl;(1-adamantylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl; (t-butylamido) dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium(II)1,4diphenyl-1,3-butadiene; (t-butylamido)dimethyl(η⁵-2,3-dimethylindenyl)silanetitanium (II)1,3-pentadiene; (t-butylamido) dimethy(η⁵-2,3-dimethylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (t-butyl amido) dimethy1(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dimethyl; (t-butylamido)dimethyl (η5-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl;(n-butylamido)diisopropoxy(η⁵-2,3-dimethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene; (n-butylamido)diisopropoxy(η5-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene;(n-butylamido)diisopropoxy(η⁵-2,3-dimethylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (n-butylamido)diisopropoxy(η⁵-2,3-dimnethylindenyl)silanetitanium (IV) dimethyl;(n-butylamido)diisopropoxy(η⁵-2,3-dimnethylindenyl)silanetitanium(IV)dibenzyl;(cyclododecylamido) diisopropoxy(η⁵-2,3-dimethylindenyl)-silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido)diisopropoxy(η⁵-2,3-dimethylindeny1)-silanetitaniun (II) 1,3-pentadiene;(cyclododecylamido) diisopropoxy(η⁵-2,3-dimethylindenyl)-silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(cyclododecylamido)diisopropoxy(η⁵-2,3-dimethylindenyl)-silanetitanium(IV) dimethyl; (cyclododecylamido)diisopropoxy(η⁵-2,3-dimethylindenyl)-silanetitanium (IV)dibenzyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3-dimethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trirethylanilido)diisopropoxy(η⁵-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene;(2,4,6-triethylanilido)diisopropoxy(η⁵-2,3dimethylin-denyl)silanetitanium(III) 2-(N,N-dimethyl amino)benzyl;(2,4,6-triethylanilido)diisopropoxy(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dimethyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)diisopropoxy(η⁵-2,3-dimethylindenyl) silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(1-adamantylamido)diisopropoxy(η⁵-2,3-dimethylindenyl) silanetitanium(II) 1,3-pentadiene;(1-adamantylamido)diisopropoxy(η⁵-2,3-dimethylindenyl) silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (1-adamantylamido)diisopropoxy(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dimethyl;(1-adamantylamido) diisopropoxy(η⁵-2,3-dimethylindenyl)silanetitanium(IV) dibenzyl; (n-butylamido) dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (n-butylamido)dinethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (II)1,3-pentadiene; (n-butylamido)dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (n-butyl amido)dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dimethyl;(n-butylamido) dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (IV)dibenzyl; (cyclododecylamido) dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene;(cyclo dodecylamido) dimethoxy(η⁵-2,3diethylindenyl)silanetitanium (II)1,3-pentadiene; (cyclo dodecylamido)dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl; (cyclododecylamido)dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (IV)dimnethyl; (cyclododecylamido)dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium. (IV) dibenzyl;(2,4,6-trimethylanilido)dimnethoxy(72⁵-2,3-dimethyl-indenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium(II) 1,3-pentadiene;(2,4,6-trimethylanilido)dimethoxy(η⁵-2,3-dimethylindenyl) silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido)dimethoxy(η⁵-2,3-dimethylindenyl) silanetitanium(IV) dimethyl; (2,4,6-trimethylanilido)dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)dimethoxy(η⁵-2,3-diinethylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene; (1-adamantylainido)dimethoxy(η⁵-2,3-dimethyl indenyl)silanetitanium (II)1,3-pentadiene; (1-adamantylamido)dimethoxy(n⁵-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethyl amino)benzyl;(1-adamantylamido)dimethoxy(η⁵-2,3-dimethylindenyl)silanetitanium(IV)dimethyl; (1-adamantylamido)dimethoxy(η5-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl;(n-butylamido)ethoxymethyl(η⁵-2,3-dimethylindenyl)-silanetitanium (II)1,4-diphenyl- 1,3-butadiene; (n-butylamido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene;(n-butylamido) ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl;(n-butylamido)ethoxymethyl(η⁵-2,3-dimethylindenyl) silane titanium (IV)dimethyl; (n-butylamido) ethoxymethyl(η⁵-2,3-dimethylindenyt)silanetitanium (IV) dibenzyl; (cyclododecylamido)ethoxymethyl(η⁵-2,3-dinethylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene; (cyclododecylamido)ethoxymethyl(η⁵-2,3-dimethyl indenyl)silanetitanium (II)1,3-pentadiene; (cyclododecylamido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl; (cyclododecylamido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dimethyl;(cyclododecyl amido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium(IV) dibenzyl;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitaniun (II) 1,3-pentadiene;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido)ethoxymethyl(η5-2,3-dimethyl indenyl)silanetitanium (IV) dimethyl;(2,4,6-trimethylanilido)ethoxyrnethyl(η⁵-2,3-dimethyl indenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)ethoxymethyl(η⁵-2,3-dimethylindenyl) silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (1-adamantylamido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantyl amido)ethoxymethy (η⁵-2,3-diinethylindenyl)silanetitanium(III) 2-(N,N-dimethyl amino)benzyl; (1-adamantylamido)ethoxymnethyl(η⁵-2,3-dimethylindenyl) silanetitanium (IV)dimnethyl; (1-adamantylamido)ethoxymethyl(η⁵-2,3-dimethylindenyl)silanetitanium (IV) dibenzyl;

3-methylindenyl complexes:

(t-butylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(t-butylamido)dimethy(η⁵-3-methylindenyl)silanetitanium (II)1,3-pentadiene; (t-butylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (t-butylamido)dimethyl(t⁵-3-methylindenyl)silanetitanium (IV) dimethyl;(t-butylamido) diMethyl(η5-3-methylindenyl)silanetitanium (IV) dibenzyl;(n-butylamido)dimethyl(η⁵-3-methylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene; (n-butylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (II) 1,3-pentadiene;(n-butylamido)dimethyl(η5-3-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (n-butylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (IV) dimethyl;(n-butylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (IV) dibenzyl;(cyclododecylamido)dimethyl(η5-3-methyl indenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(cyclododecylamido)dimethyl(15-3-methylindenyl)silanetitanium (II)1,3-pentadiene;(cyclododecylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (III)2-(N,N-dimethyl amino)benzyl; (cyclododecylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (IV) dimethyl;(cyclododecylamido) dimethy (n⁵-3-methylindenyl)silanetitanium (IV)dibenzyl; (2,4,6-tinethylanilido)dimethyl(η⁵-3-methylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)dimethyl(η⁵-3-methylindenyl)silanetitanium (II)1,3-pentadiene;(2,4,6-trimethylanilido)dimethyl(η5-3-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl;(2,4,6-trimethylanilido)dimethyl(η⁵-3-methylindenyl)silanetitanium (IV)dimethyl; (2,4,6-triethylanilido)dimethy(η⁵-3-methylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)dimethyl(η⁵-3-methylindenyl)silanetitaniuin (II)1,4-diphenyl-1,3-butadiene;(1-adamantylainido)dimethyl(η⁵-3-methylindenyl)silanetitanium (I)1,3-pentadiene;(1-adamantylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl;(1-adamantylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (IV)dimethyl; (1-adamantylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium(IV) dibenzyl; (t-butyl amido)dimethyl(η⁵-3-methylindenyl)silanetitanium(II) 1,4-diphenyl- 1,3-butadiene; (t-butylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (II) 1,3-pentadiene;(t-butylamido) dimethyl (η⁵-3-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (t-butylamido)dimethyl(η⁵-3-methylindenyl)silanetitanium (IV) dimethyl; (t-butylamido)dimethy(r⁵-3-methylindenyl) silanetitanium (IV) dibenzyl;(n-butylamido)diisopropoxy(η⁵-3-methylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(n-butylamido)diisopropoxy(η⁵-3-methylindenyl)silanetitanium (II)1,3-pentadiene;(n-butylamido)diisopropoxy(η⁵-3-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl;(n-butylamido)diisopropoxy(η⁵-3-methylindenyl)silanetitanium (IV)dimethyl; (n-butylamido)diisopropoxy(η⁵-3-methylindenyl)silanetitanium(IV) dibenzyl;(cyclododecylamido)diisopropoxy(η⁵-3-methylindenyl)-silanetitanium (II)1,4-diphenyl- 1,3-butadiene;(cyclododecylamido)diisopropoxy(η⁵-3-methylindenyl)-silanetitanium (II)1,3-pentadiene;(cyclododecylamido)diisopropoxy(η⁵-3-methylindenyl)-silanetitanium (III)2-(N,N-dimethylamino)benzyl;(cyclododecylamido)diisopropoxy(η⁵-3-methylindenyl)-silanetitanium (IV)dimethyl;(cyclododecylamido)diisopropoxy(η⁵-3-methylindenyl)-silanetitanium (IV)dibenzyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-3-methyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)diisopropoxy(η⁵-3-methylindenyl)silanetitanium (II) 1,3-pentadiene;(2,4,6-trimethylanilido) diisopropoxy(η⁵-3-methylin-denyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-3-methylindenyl) silanetitanium(IV) dimnethyl; (2,4,6-trimethylanilido)diisopropoxy(η⁵-3-methylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)diisopropoxy(η⁵-3-methylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene; (1-adamntylarido)diisopropoxy(η⁵-3-methylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylamido)diisopropoxy(η⁵-3-methyl indenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (1-adamantylamido)diisopropoxy(η⁵-3-methylindenyl) silanetitanium (IV) dimethyl;(1-adamantylamido)diisopropoxy(η⁵-3-methylindenyl) silanetitanium (IV)dibenzyl; (n-butylamido)dimethoxy(η⁵-3-methylindenyl) silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(n-butylamido)dimethoxy(η⁵-3-methylindenyl) silanetitanium (II)1,3-pentadiene;(n-butylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl;(n-butylamido)dimethoxy(η⁵-3-methylindenyl)silane titanium (IV)dimethyl; (n-butylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium (IV)dibenzyl; (cyclododecylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium(II) 1,4diphenyl-1,3-butadiene;(cyclododecylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium (II)1,3-pentadiene;(cyclododecylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium (II)2-(N,N-dimethylamino)benizyl;(cyclododecylamido)dimethoxy(η⁵-3-methylindenyl) silane titanium (IV)dimethyl; (cyclododecylamido)didethoxy(η⁵-3-methylindenyl)silanetitanium (IV) dibenzyl;(2,4,6-trimethylanilido)dimethoxy(η⁵-3-methylindenyl) silanetitanium(11) 1,4-diphenyl-1,3-butadiene,(2,4,6-trimethylanilido)dimethoxy(η⁵-3-methyhindenyl) silane ttanium(II) 1,3-pentadiene;(2,4,6-trimethylanilido)dimethoxy(η⁵-3-methylindenyl) silane titanium(III) 2-(N,N-dimethylamino)benzyl;(2,4,6-triethylanilido)dimethoxy(η⁵-3-methylindenyl)silanetitanium (IV)dimethyl;(2,4,6-trimethylanilido)dimethoxy(η⁵-3-methylindenyl)silanetitanium (IV)dibenzyl; (1-adamantylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (1-adamantylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylamido) dimethoxy(η⁵-3-methylindenyl)silanetitanium, (III)2-(N,N-dimethylamino)benzyl;(1-adamantylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium (IV)dimethyl; (1-adamantylamido)dimethoxy(η⁵-3-methylindenyl)silanetitanium(IV) dibenzyl;(n-butylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(n-butylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium (II)1,3-pentadiene;(n-butylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium (III)2-(N,N-dimethyl amino)benzyl; (n-butylamido)ethoxymethy(η⁵-3-methylindenyl)silanetitanium (IV) dimethyl;(n-butylamido)ethoxymethyl(il⁵-3-methylindenyl)silanetitanium (IV)dibenzyl; (cyclododecylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene; (cyclododecylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium (II)1,3-pentadiene; (cyclododecylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl;(cyclododecylamido)ethoxymethyl(η⁵-3-methylindenyl) silane titanium (IV)dimethyl; (cyclododecylamido)ethoxymethyl(η⁵-3-methylindenyl) silanetitanium (IV) dibenzyl; (2,4,6-trimethylanilido)ethoxymethyl(η5-3-methylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-3-methylindenyi)silanetitanium(II) 1,3-pentadiene; (2,4,6-trimethylanilido)ethoxymethy(η⁵-3-methylindenyi)silanetitanium (III) 2-(N,N-dimethyl amino)benzyl;(2,4,6-triethylanilido)ethoxymethy (η⁵-3-methylindenyl)silanetitanium(IV) dimethyl;(2,4,6-trimethylaniiido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium(IV) dibenzyl;(1-adamantylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(1-adamantylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium (II)1,3-pentadiene;(1-adamantylamido)ethoxymethyl(η⁵-3-methylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(1-adamantylamidb)ethoxymethyl(η⁵-3-methylindenyl)silane titanium (IV)dimethyl; (1-adamantylamido)ethoxymethy(η⁵-3-methylindenyl)silanetitanium (IV) dibenzyl;

2-methyl-3-ethylindenyl Complexes:

(t-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-buta diene;(t-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II)1,3-pentadiene; (t-butylamido)dimethy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(t-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyi)silanetitanium (IV)dimethyl; (t-butylamido)dimethy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl; (n-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)-silanetitanium (II)1,4-diphenyl-1,3-butadiene;(n-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II)1,3-pentadiene; (n-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyt)-silanetitanium (III)2-(N,N-dimethylamino)benzyl;(n-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl) silane titanium (IV)dimethyl; (n-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl;(cyclododecylamido) dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl) silanetitanium (II)1,3-pentadiene; (cyclododecylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (III)2-(N,N-dimethyl amino) benzyl; (cyclododecylamido)dimethyl(−2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(cyclododecyl amido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(IV) dibenzyl;(2,4,6-trimethylanilido)dimethyl(η⁵-2-methyl-3-ethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(II) 1,3-pentadiene;(2,4,6-trimethylanilido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(II) 2-(N,N-diethylamio)benzy;(2,4,6-trimethylaninido)didethyl(η⁵-2-methyl -3-ethylindenyl)silanetitanium (IV) dimethyl;(2,4,6-triethylanilido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl) silanetitanium(II) 1,4diphenyl-1,3-butadiene; (1-adamantylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylamido) dimiethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (1-adamantylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(1-adaamantylamido) dimethyl(n5-2-methyl-3-ethylindenyl)silanetitanium(IV) dibenzyl;(t-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)-silanetitanium (II)1,4-diphenyl-1,3-butadiene; (t-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene;(t-butylamido)dimethyl(η⁵-2-methyl-eththylindenyl)-silanetitanium (III)2-(N,N-dimethylamino)benzyl; (t-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(t-butylamido)dimethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV)dibenzyl;(n-butylamido)diisopropoxy(η⁵-2-methyl-3-ethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(n-butylamido)diisopropoxy(η⁵-2-rmethyl-3-ethylindenyl) silane titanium(II) 1,3-pentadiene;(n-butylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl) silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (n-butylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(n-butylamido) diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(IV) dibenzyl; (cyclododecylamido)diisopropoxy(−2-methyl-3-ethyl-indenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene; (cyclododecylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)-silanetitanium(II) 1,3-pentadiene;(cyclododecylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)-silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(cyclododecylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)-silanetitanium (IV) dimethyl;(cyclododecylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)-silanetitanium(IV) dibenzyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(II) 1,3-pentadiene; (2,4,6-timethylanilido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (2,4,6-trimethylanilido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(IV) dimnethyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(IV) dibenzyl;(1-adamantylamido)diisopropoxy(η⁵-2-methyl-3-ethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (1-adamantylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II)1,3-pentadiene;(1-adamantylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(1-adamantylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl) silanetitanium (IV) dimethyl;(1-adamantylamido)diisopropoxy(η⁵-2-methyl-3-ethylindenyl) silanetitanium (IV) dibenzyl;(n-butylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silane titanium (II)1,4-diphenyl-1,3-butadiene;(n-butylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl) silanetitanium (II)1,3-pentadiene; (n-butylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (HI) 2-(N,N-dimethylamino)benzyl;(n-butylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV)dimnethyl;(n-butylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV)dibenzyl;(cyclododecylamido)dimethoxy(η⁵-2-methyl-3-ethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene;(cyclododecyl amido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino) benzyl; (cyclododecylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl) silanetitanium (IV) dimethyl;(cyclododecylamido) dimethoxy(η⁵-2-methyl-3-ethylindenyl) silanetitanium(IV) dibenzyl; (2,4,6-trimethylanilido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)dimethoxy(η⁵-2-methyl-3-ethylindenyl) silanetitanium (II)1,3-pentadiene; (2,4,6-trimethylanilido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido) dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl; (2,4,6-trimethylanilido)dimethoxy(η⁵-2-methyl-3-ethylindenyl) silanetitanium (IV)dibenzyl; (1-adamantylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl- 1,3-butadiene;(1-adamantylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(II) 1,3-pentadiene;(1-adamantylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (1-adamantylamido)dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(1-adamantylamido) dimethoxy(η⁵-2-methyl-3-ethylindenyl)silanetitanium(IV) dibenzyl; (n-butylamido)ethoxymethyl(η⁵-2-methyl-3-ethyl-inmdenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene; (n-butylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene;(n-butylamido)ethoxy methyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(I) 2-(N,N-dimethyl amino)benzyl; (n-butylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(n-butylanido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(IV) dibenzyl;(cyclododecylamido)ethoxymethyl(η⁵-2-methyl-3-ethyl-indenyl)silane-titanium(II) 1,4-diphenyl-1,3-butadiene;(cyclododecylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II) 1,3-pentadiene;(cyclododecylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silane-titanium (III) 2-(N,N-dinethylamino)benzyl; (cyclododecylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(cyclododecylamido)ethoxyamethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV)dibenzyl;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(II) 1,4diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl) silanetitanium (II)1,3-pentadiene; (2,4,6-trimethylanilido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido) ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (II) 1,4-diphenyl- 1,3-butadiene;(1-adamantylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium(II) 1,3-pentadiene;(1-adamantylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl; (1-adamantylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dimethyl;(1-adamantylamido)ethoxymethyl(η⁵-2-methyl-3-ethylindenyl)silanetitanium (IV) dibenzyl;

2,3,4,6tetramethylindenyl Complexes:

(t-butylamido)dimethyl(η5-2,3,4,6-tetramethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(t-butylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II)1,3-pentadiene;(t-butylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(t-butylamido)dimethyl(η⁵2,3,4,6-tetramethylindenyl)silane titanium (IV)dimethyl;t-butylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV)dibenzyl;(n-butylamido)dinethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(n-butylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silane titanium(II) 1,3-pentadiene;(n-butylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)-silane titanium(III) 2-(N,N-dimethylamino)benzyl;(n-butylamido)dimethyl(η⁵-2,3,4,6-tetra methylindenyl)silanetitanium(IV) dimethyl; (n-butylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl;(cyclododecylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene;(cyclododecylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene;(cyclododecylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl) silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(cyclododecylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl;(cyclododecylamido)dinethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl;(2,4,6-trimethylanilido)dimethyl(η⁵-2,3,4,6-tetramnethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)dinethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II)1,3-pentadiene; (2,4,6-trimethylanilido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(III) 2-(N,N-dimethyl amino)benzyl;(2,4,6-trimethylanilido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimnethyl;(2,4,6-trimethylanilido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylainido)dimethyl(η⁵-2,3,4,6,-tetramethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(1-adamantylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silane titanium(II) 1,3-pentadiene;(1-adamantylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl) silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(1-adamantylamido)dimethyl(η⁵-2,3,4,6-tetra methylindenyl)silanetitanium(IV) dimethyl; (1-adamantylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl;(t-butylamido)dimethyl(η⁵-2,3,4,6-tetramethyl indenyl)-silanetitanium(II) 1,4-diphenyl- 1,3-butadiene; (t-butylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II)1,3-pentadiene; (t-butylamido)dimethyl(η⁵-2,3,4,6-tetramethylindenyl)-silanetitanium (III)2-(N,N-dimethylamino)benzyl; (t-butylamido)dimethyl(η⁵-2,3,4,6-tetrarethylindenyl)silanetitanium (IV) dimethyl;(t-butylarmido)dimnethyl (11-2,3,⁴,⁶-tetramethylindenyl)silanetitanium(IV) dibenzyl;(n-butylado)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silane-titanium(II) 1,4-diphenyl-1,3-butadiene; (n-butylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silane-titanium (II)1,3-pentadiene; (n-butylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)-silanetitanium (III)2-(N,N-dimethylamino)benzyl;(n-butylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silane-titanium (I) dimethyl;(n-butylamido)diisopropoxy(η⁵-2,3,4,6-tetrarnethylindenyl)silane-titanium (IV) dibenzyl; (cyclododecylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)-silanetitanium(II)1,4-diphenyl-1,3-butadiene; (cyclododecylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitaniuim (II)1,3-pentadiene; (cyclododecylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl;cyclododecylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl;(cyclododecylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl;(2,4,6-trimethylamlido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II)1,3-pentadiene; (2,4,6-trimethylanilido)diisopropoxy(71⁵-2,3,4,6-tetramethylindenyl)silanetitanium (III)2-(N,N-dimethylamino) benzyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(IV) dibenzyl;(1-adamnantylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(1-adamantylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (1-adamantylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV)dimethyl; (1-adamantylamido)diisopropoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV)dibenzyl; (n-butylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(n-butylamido)dimethoxy(η5-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,3-pentadiene;(n-butylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(III) 2-(N,N-dimethyl amino)benzyl;(n-butylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(IV) dimethyl;(n-butylamido)dimethoxy(η5-2,3,4,6-tetramethylindenyl)silanetitanium(IV) dibenzyl;(cyclododecylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(cyclododecylamido)dimethoxy(η5-2,3,4,6-tetrarnethylindenyl)silanetitanium (II) 1,3-pentadiene;(cyclododecylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N dimethylamino)benzyl;(cyclododecylamido) dimethoxy(η⁵-2,3,4,6-tetramethyl*indenyl)silanetitanium (IV) dimethyl; (cyclododecylamido)dimethoxy(η⁵-2,3,4,6-tetramethyl indenyl)silanetitanium (IV) dibenzyl;(2,4,6-trimethylanilido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,4-diphenyl-1,3-butadiene;(2,4,6-triethylanilido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene; (2,4,6-trimethylanilido) dimethoxy(η⁵-2,3,4,6-tetramethyl indenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (2,4,6-trimethylanilido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl;(2,4,6-trimethylanilido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(IV) dibenzyl;(1-adamantylamido)dinethoxy(η5-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(1-adamantylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,3-pentadiene;(1-adamantylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(1-adanantylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl;(1-adamantylamido)dimethoxy(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) -dibenzyl;(n--butylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (n-butylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II) 1,3-pentadiene;(n-butylamido)ethoxymethyl (η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(III) 2-(N,-dimethylamino)benzyl;(n-butylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silane titanium(IV) dimethyl;(n-butylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silane titanium(IV) dibenzyl; (cyclododecylamido)ethoxymethy1(η⁵-2,3,4,6-tetramethylindenyl) silanetitanium (II)1,4-diphenyl-1,3-butadiene; (cyclododecylamido)ethoxymethy(η⁵-2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene;(cyclododecylamido) ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(cyclododecylamido)ethoxymethyl (η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl; (cyclododecylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethyfindenyl)silanetitanium (IV) dibenzyl;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,3-pentadiene;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (1-adamantylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl) silanetitanium (II)1,3-pentadiene; (1-adamantylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(1-adamantylamido) ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dimethyl; and(1-adamantylamido)ethoxymethyl(η⁵-2,3,4,6-tetramethylindenyl)silanetitanium (IV) dibenzyl.

2,3,4,6,7-pentamethylindenyl Complexes:

(t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,3-pentadiene;(t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(I) 2-(N,N-dimethylamino)benzyl;(t,butylamidodimethyl(η⁵-2,3,4,6,7-pentamethylindenyl) silanetitanium(IV) dimethyl; (t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl;(n-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(n-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,3-pentadiene;(n-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)-silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (n-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl;(n-butylamido) dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silane titanium(IV) dibenzyl; (cyclododecylamido)dinethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silane titanium (II)1,4-diphenyl-1,3-butadiene;(cyclododecylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene;(cyclododecylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl; (cyclododecylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dimethyl; (cyclododecylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dibenzyl;(2,4,6-trimethylanilido)dimethyl(η⁵-2,3,4,6,7-pentamethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene;(2,4,6-trimethylaniiido)dimethyl(η⁵-2,3,4,6,7-pentamethyl-indenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl; (2,4,6-trimethylanilido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (I) dimethyl;(2,4,6-trimethylanilido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(IV) dibenzyl;(1-adamantylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II)1,4-diphenyl-1,3-butadiene; (1-adamantylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylamido) dimethyl(η5-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(1-adamantylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(IV) dimethyl;(1-adamantylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(IV) dibenzyl;(t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentarmethylindenyl)-silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,3-pentadiene;(t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)-silanetitanium(III) 2-(N,N-dimethylamio)benzyl;(t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl) silane titanium(IV) dimethyl; (t-butylamido)dimethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl;(n-butylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethyl-indenyl)silane-titanium (II) 1,4-diphenyl-1,3-butadiene;(n-butylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silane-titanium(II) 1,3-pentadiene;(n-butylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)-silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(n-butylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silane-titanium(IV) dimethyl;(n-butylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silane-titanium(IV) dibenzyl;(cyclododecylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethyl-indenyl)-silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(cyclododecylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene;(cyclododecylamido)diisopropoxy(−2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(cyclododecylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dimethyl; (cyclododecylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dibenzyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(2,4,6-timethylanilido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silane titanium (II) 1,3-pentadiene;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dimethyl; (2,4,6-trimethylanilido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl) silanetitanium(IV) dibenzyl;(1-adamantylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(1-adamantylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(1-adamantylamido) diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl; (1-adamantylamido)diisopropoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dibenzyl;(n-butylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene; (n-butylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitaniumn (II)1,3-pentadiene;(n-butylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl; (n-butylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silane titanium (IV) dimethyl;(n-butylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silane titanium(IV) dimethyl;(n-butylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanesilanetitanium (II) 1,4-diphenyl-1,3-butadiene;(cyclododecylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,3-pentadiene;(cyclododecylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitaniun(III) 2-(N,N-dimethylamino)benzyl; (cyclododecylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dimethyl;(cyclododecylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(IV) dibenzyl; (2,4,6-trimethylanilido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silane titanium (II)1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene; (2,4,6-trimethylanilido)dimethoxy(η⁵-2,3,4,6,7-pentamethyl indenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (2,4,6-triethylanilido)dimethoxy(η⁵-2,3,4,6,7-pentamethyl indenyl)silanetitanium (IV)ditnethyl; (2,4,6-trimethylanilido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dibenzyl; (1-adamantyl amido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II)1,4-diphenyl-1,3-butadiene;(1-adamantylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,3-pentadiene;(1.-adamantylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl;(1-adamantylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl;(1-adamantylamido)dimethoxy(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl;(n-butylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(n-butylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,3-pentadiene; (n-butylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (III)2-(N,N-dimethylamino)benzyl; (n-butylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dimethyl; (n-butylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dibenzyl; (cyclododecylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(cyclododecylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene;(cyclododecylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(cyclododecylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl;(cyclododecylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dibenzyl;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silane titanium (II) 1,3-pentadiene; (2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethyl indenyl)silanetitanium (III)2-(N,N-dimnethylamino)benzyl; (2,4,6-triethylanilido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV)dimethyl;(2,4,6-trimethylanilido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dibenzyl;(1-adamantylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethyl-indenyl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;(1-adamantylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (II) 1,3-pentadiene;(1-adamantylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (III) 2-(N,N-dimethylamino)benzyl;(1-adamantylamido) ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium (IV) dimethyl; and(1-adamantylamido)ethoxymethyl(η⁵-2,3,4,6,7-pentamethylindenyl)silanetitanium(IV) dibenzyl.

Other catalysts, cocatalysts, catalyst systems, and activatingtechniques which may be used in the practice of the invention disclosedherein may include those disclosed in WO 96/23010, published on Aug. 1,1996, the entire disclosure of which is hereby incorporated byreference; those disclosed in WO 99/14250, published Mar. 25, 1999, theentire disclosure of which is hereby incorporated by reference; thosedisclosed in WO 98/41529, published Sept. 24, 1998, the entiredisclosure of which is hereby incorporated by reference; those disclosedin WO 97/42241, published Nov. 13, 1997, the entire disclosure of whichis hereby incorporated by reference; those disclosed by Scollard, etal., in J. Am. Chem. Soc 1996, 118, 10008-10009, the entire disclosureof which is hereby incorporated by reference; those disclosed in EP 0468 537 B1, published Nov. 13, 1996, the entire disclosure of which ishereby incorporated by reference; those disclosed in WO 97/22635,published Jun. 26, 1997, the entire disclosure of which is herebyincorporated by reference; those disclosed.in EP 0 949 278 A2, publishedOct. 13, 1999, the entire disclosure of which is hereby incorporated byreference; those disclosed in EP 0 949 279 A2, published Oct. 13, 1999,the entire disclosure of which is hereby incorporated by reference;those disclosed in EP 1 063 244 A2; published Dec. 27, 2000, the entiredisclosure of Which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 5,408,017, the entire disclosure of which is herebyincorporated by reference; those disclosed in U.S. Pat. No. 5,767,208,the entire disclosure of which is hereby incorporated by reference,those disclosed in U.S. Pat. No. 5,907,021, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in WO88/05792, published Aug. 11, 1988, the entire disclosure of which ishereby incorporated by reference; those disclosed in WO88/05793,published Aug. 11, 1988, the entire disclosure of which is herebyincorporated by reference; those disclosed in WO 93/25590, publishedDec. 23, 1993, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,599,761, the entiredisclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 5,218,071, the entire disclosure of which is herebyincorporated by reference; those disclbsed in WO 90/07526, publishedJuly 12, 1990, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,972,822, the entire.disclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 6,074,977, the entire disclosure of which is herebyincorporated by reference; those disclosed in U.S. Pat. No. 6,013,819,the entire disclosure of which is hereby incorporated by reference;those disclosed in U.S. Pat. No. 5,296,433, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in U.S. Pat.No. 4,874,880, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,198,401, the entiredisclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 5,621,127, the entire disclosure of which is herebyincorporated by reference; those disclosed in U.S. Pat. No. 5,703,257,the entire disclosure of which is hereby incorporated by reference;those disclosed in U.S. Pat. No. 5,728,855, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in U.S. Pat.No. 5,731,253, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,710,224, the entiredisclosure of which is hereby incorporated by reference; those disclosedin U.S. Pat. No. 5,883,204, the entire disclosure of which is herebyincorporated by reference; those disclosed in U.S. Pat. No. 5,504,049,the entire disclosure of which is hereby incorporated by reference;those disclosed in U.S. Pat. No. 5,962,714, the entire disclosure ofwhich is hereby incorporated by reference; those disclosed in U.S. Pat.No. 5,965,677, the entire disclosure of which is hereby incorporated byreference; those disclosed in U.S. Pat. No. 5,427,991, the entiredisclosure of which is hereby incorporated by reference; those disclosedin WO 93/21238, published Oct. 28, 1993, the entire disclosure of whichis hereby incorporated by reference; those disclosed in WO 94/03506,published Feb. 17, 1994, the entire disclosure of which is herebyincorporated by reference; those disclosed in WO 93/21242, publishedOct. 28, 1993, the entire disclosure of which is hereby incorporated byreference; those disclosed in WO 94/00500, published Jan. 6, 1994, theentire disclosure of which is hereby incorporated by reference; thosedisclosed in WO 96/00244, published Jan. 4, 1996, the entire disclosureof which is hereby incorporated by reference; those disclosed in WO98/50392, published Nov. 12, 1998, the entire disclosure of which ishereby incorporated by reference; those disclosed in Wang, et al.,Organometallics 1998, 17, 3149-3151, the entire disclosure of which ishereby incorporated by reference; those disclosed in Younkin, et al.,Science 2000, 287, 460462, the entire disclosure of which is herebyincorporated by reference; those disclosed by Chen and Marks, Chem. Rev.2000, 106, 1391-1434, the entire disclosure of which is herebyincorporated by reference; those disclosed by Alt and Koppl, Chem. Rev.2000, 100, 1205-1221, the entire disclosure of which is herebyincorporated by reference; those disclosed by Resconi, et al., Chem.Rev. 2000, 100, 1253-1345, the entire disclosure of which is herebyincorporated by reference; those disclosed by Ittel, et al., ChemRev.2000, 100, 1169-1203, the entire disclosure of which is herebyincorporated by reference; those disclosed by Coates, Chem. Rev., 2000,100, 1223-1251, the entire disclosure of which is hereby incorporated byreference; and those disclosed in WO 96/13530, published May 9, 1996,the entire disclosure of which is hereby incorporated by reference. Alsouseful are those catalysts, cocatalysts, and catalyst systems disclosedin U.S. Ser. No. 09/230,185, filed Jan. 15, 1999; U.S. Pat. Nos.5,965,756; 6,150,297; U.S. Ser. No. 09/715,380, filed Nov. 17, 2000.

Methods for preparing the aforementioned catalysts are described, forexample, in U.S. Patent No. 6,015,868. In some embodiments, thefollowing catalysts are used: 1)(N-1,1-dimethylethyl)-1,1-(methylphenyl)-1-((1,2,3,3a,7a-n)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium;and 2)(N-1,1-dimethylethyl)-1,1-(4-butylphenyl)-1-((1,2,3,3a,7a-n)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-) dimethyltitanium. The chemical structures ofcertain of these catalysts are illustrated in FIG. 1.

Cocatalysts:

The above-described catalysts may be rendered catalytically active bycombination with an activating cocatalyst or by use of an activatingtechnique. Suitable activating cocatalysts for use herein include, butare not limited to, polymeric or oligomeric alumoxanes, especiallymethylalumoxane, triisobutyl aluminum modified methylalumoxane, orisobutylalumoxane; neutral Lewis acids, such as C₁₋₃₀ hydrocarbylsubstituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- ortri(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 30 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more especiallyperfluorinated tri(aryl)boron and perfluorinated tri(aryl)aluminumcompounds, mixtures of fluoro-substituted(aryl)boron compounds withalkyl-containing aluminum compounds, especially mixtures oftris(pentafluorophenyl)borane with trialkylaluminum or mixtures oftris(pentafluorophenyl)borane with alkylalumoxanes, more especiallymixtures of tris(pentafluorophenyl)borane with methylalumoxane andmixtures of tris(pentafluorophenyl)borane with methylalumoxane modifiedwith a percentage of higher alkyl groups (MMAO), and most especiallytris(pentafluorophenyl)borane and tris(pentafluorophenyl)aluminum;non-polymeric, compatible, non-coordinating, ion forming compounds(including the use of such compounds under oxidizing conditions),especially the use of ammonium-, phosphonium-, oxonium-, carbonium-,silylium- or sulfonium- salts of compatible, non-coordinating anions, orferrocenium salts of compatible, non-coordinating anions; bulkelectrolysis and combinations of the foregoing activating cocatalystsand techniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes in the following references: EP-A-277,003, U.S. Pat. Nos.5,153,157, 5,064,802, EP-A-468,651 (equivalent to U.S. Ser. No.07/547,718), EP-A-520,732 (equivalent to U.S. Ser. No. 07/876,268), andEP-A-520,732 (equivalent to U.S. Ser. Nos. 07/884,966 filed May 1,1992). The disclosures of the all of the preceding patents or patentapplications are incorporated by reference herein in their entirety.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. It has been observedthat the most efficient catalyst activation using such a combination oftris(pentafluoro-phenyl)borane/alumoxane mixture occurs at reducedlevels of alumoxane. Preferred molar ratios of Group 4 metalcomplex:tris(pentafluoro-phenylborane:alumoxane are from 1:-1:1 to1:5:10, more preferably from 1:1:1 to 1:3:5. Such efficient-use of lowerlevels of alumoxane allows for the production of olefin polymers withhigh catalytic efficiencies using less of the expensive alumoxanecocatalyst. Additionally, polymers with lower levels of aluminumresidue, and hence greater clarity, are obtained.

Suitable ion forming compounds useful as cocatalysts in some embodimentsof the invention comprise a cation which is a Bronsted acid capable ofdonating a proton, and a compatible, non-coordinating anion, A⁻. As usedherein, the term “non-coordinating” means an anion or substance whicheither does not coordinate to the Group 4 metal containing precursorcomplex and the catalytic derivative derived therefrom, or which is onlyweakly coordinated to such complexes thereby remaining sufficientlylabile to be displaced by a neutral Lewis base. A non-coordinating anionspecifically refers to an anion which, when functioning as a chargebalancing anion in a cationic metal complex, does not tnansfer ananionic substituent or fragment thereof to the cation thereby formingneutral complexes during the time which would substantially interferewith the intended use of the cationic metal complex as a catalyst.“Compatible anions” are anions which are not degraded to neutrality whenthe initially formed complex decomposes and are non-interfering withdesired subsequent polymerization or other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, the anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, known in theart and many, particularly such compounds containing a single boron atomin the anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:(L*—H)_(d) ⁺(A)^(d−)  Formula VIIwherein L* is a neutral Lewis base; (L*—H)+is a Bronsted acid; A^(d−) isananion having a charge of d−, and d is an integer from 1 to 3. Morepreferably A^(d−) corresponds to the formula: [M′Q₄]⁻, wherein M′ isboron or aluminum in the +3 formal oxidation state; and Q independentlyeach occurrence is selected from hydride, dialkylamido, halide,hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl,halosubstituted hydrocarbyloxy, and halo-substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl- perhalogenatedhydrocarbyloxy- and perhalogenated silyihydrocarbyl radicals), the Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:(L*—H)⁺(M′Q₄)⁻;  Formula VIIIwherein L* is as previously defined; M′ is boron or aluminum in aforrnal oxidation state of 3; and Q is a hydrocarbyl-, hydrocarbyloxy-,fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinatedsilylhydrocarbyl- group of up to 20 non-hydrogen atoms, with the provisothat in not more than one occasion is Q hydrocarbyl. Most preferably, Qin each occurrence is a fluorinated aryl group, especially apentafluorophenyl group. Preferred (L*—H)⁺ cations areN,N-dimethylanilinium, N,N-di(octadecyl)anilinium,di(octadecyl)methylammonium, methylbis(hydrogenated tallowyl)amrnmonium,and tributylammonium.

Illustrative, but not limiting, examples of boron compounds which maybeused as an activating cocatalyst are tri-substituted ammonium salts suchas: trimethylammonium tetrais(pentafluorophenyl) borate;triethylarnmonium tetrais(pentafluorophenyl) borate; tripropylammoniumtetrakis (pentafluorophenyl) borate; tri(n-butyl)ammoniumtetrakis(pentafluorophenyl) borate; tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl) borate; N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate; N,N-dimethylaniliniumn-butyltris(pentafluorophenyl) borate; N,N-dimethylaniliniumbenzyltris(pentafluorophenyl) borate; N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5, 6-tetrafluorophenyl) borate;N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl) borate;N,N-dimethylanilinium pentafluoro phenoxytris(pentafluorophenyl) borate;N,N-diethylanilinium tetrakis(pentafluorophenyl) borate;N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)-borate; trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate;triethylanrnonium tetrakis(2,3,4,6-tetrafluorophenyl) borate;tripropylammonium tetrkis(2,3,4,6-tetrafluorophenyl) borate;tri(n-butyl)armoniurn tetrakis(2,3,4,6-tetrafluorophenyl) borate,dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetra fluorophenyl) borate;N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate;N,N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate; andN,N-dimethyl-2,4,6-trimethylaniliniumtetrakis(2,3,4,6-tetrafluorophenyl) borate; dialkyl ammonium salts suchas: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, anddicyclohexylammonium tetrakis(pentafluorophenyl) borate; tri-substitutedphosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphoniurmtetrakis(pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate;di-substituted oxonium salts such as: diphenyloxoniumteakis(pentafluorophenyl) borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and di(2,6-dimethylphenyl)oxoniumtetrakis(pentafluorophenyl) borate; di-substituted sulfonium salts suchas: diphenylsulfonium tetrakis(pentafluorophenyl) borate,di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, andbis(2,6-dimethylphenyl) sulfonium tetrais(pentafluorophenyl) borate.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a non-coordinating, compatible anionrepresented by the formula:(Ox^(e+))_(d)(A^(d−))_(e)  Formula IXwherein: Ox³⁺ is a cationic oxidizing agent having a charge of e+; e isan integer from 1 to 3; and A^(d−) and d are as previously defined.

Examples of cationic oxidizing agents include, but are not limited to,ferrocenium, hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺².Preferred embodiments of A^(d−) are those anions previously defined withrespect to the Bronsted acid containing activating cocatalysts,especially tetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a non-coordinating, compatibleanion represented by the formula: {circle over (C)}⁺ A⁻, wherein {circleover (C)}⁺ is a C₁₋₂₀ carbenium ion; and A⁻ is as previously defined. Apreferred carbenium ion is the trityl cation, that istriphenylmethyliuin.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silyliiim ion and a non-coordinating,compatible anion represented by the formula:R₃Si(X′)_(q) ⁺A⁻  Formula Xwherein: R is C₁₋₁₀ hydrocarbyl, and X′, q and A are as previouslydefined.

Preferred silylium salt activating cocatalysts include, but are notlimited to, trinmethylsilylium tetrakispentafluorophenylborate,triethylsilylium tetrakispentafluorophenylborate and ether substitutedadducts thereof. Silylium salts have been previously genericallydisclosed in J. Chem. Soc. ChenL Comm., 1993, 383-384, as well asLambert, J. B., et al., Organometallics, 1994, 13, 2430-2443. The use ofthe above silylium salts as activating cocatalysts for additionpolymerization catalysts is disclosed in U.S. Pat. No. 5,625,087, whichis incorporated by reference herein in its entirety. Certain complexesof alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used in embodiments of the invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433, which is also incorporated byreference herein in its entirety.

The catalyst system may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent in whichpolymerization will be carried out by solution polymerizationprocedures. The catalyst system may also be prepared and employed as aheterogeneous catalyst by adsorbing the requisite components on acatalyst support material such as silica gel, alumina or other suitableinorganic support material. When prepared in heterogeneous or supportedform, it is preferred to use silica as the support material. Theheterogeneous form of the catalyst system may be employed in a slurrypolymerization. As a practical limitation, slurry polymerization takesplace in liquid diluents in which the polymer product is substantiallyinsoluble. Preferably, the diluent for slurry polymerization is one ormore hydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orin part as the diluent. Likewise the α-olefin monomer or a mixture ofdifferent α-olefin monomers may be used in whole or part as the diluent.Most preferably, the major part of the diluent comprises at least thea-olefin monomer or monomers to be polymerized.

At all times, the individual ingredients, as well as the catalystcomponents, should be protected from-oxygen and moisture. Therefore, thecatalyst components and catalysts should be prepared and recovered in anoxygen and moisture free atmosphere. Preferably, therefore, thereactions are performed in the presence of a dry, inert gas such as, forexample, nitrogen or argon.

The amount of long chain branching can be influenced by the catalystselection as well as the specifics of the process conditions used in thenovel process described herein. The amount of long chain branching (interms of LCB per 1000 carbon atoms of the polymer) generally increaseswith higher levels of vinyl-terminated polymer chains. Because differentcatalysts exhibit different levels of vinyl termination relative toother forms of termination, a catalyst having a higher level of vinyltermination preferably should be selected in order to increase theamount of long-chain branching. Preferably, the ratio, R_(v), of vinylterminated chains to the sum of all of the thermally-induced unsaturatedchain ends (for example, vinyl+vinylidene+cis+trans for anethylene/alpha olefin copolymer) should be as high as possible. TheR_(v) ratio is defined by the equation:$R_{v} = \frac{\text{[vinyl]}}{\text{[vinyl]} + \text{[vinylidene]} + \text{[cis]} + \text{[trans]}}$wherein [vinyl] is the concentration of vinyl groups in the isolated.polymer in vinyls/1,000 carbon atoms; [vinylidene], [cis], and [trans]are the concentration of vinylidene, cis and trans groups in theisolated polymer in amount/1,000 carbon atoms, respectively. Thedetermination of unsaturated chain ends can be accomplished by methodswhich are known in the art, including preferably NMR spectroscopy,particularly ¹³C NMR spectroscopy, and most preferably ¹H NMRspectroscopy. An example of the use of ¹H NMR spectroscopy to quantifyunsaturated chain ends in ethylene/alpha olefin copolymers is given inHasegawa, et al. (J. Poly. Sci., Part A, Vol 38 (2000), pages 4641-4648), the disclosure of which is incorporated herein by reference.

In order to obtain a polymer product with relatively higher levels ofLCB, catalysts preferably should be chosen that produce high levels ofvinyl terminated chains. Preferably, the ratio of the vinyl groups tothe sum of all ofthe terminal unsaturations, R_(v) is relatively high.In some embodiments, 5 to about 50 of the polymer chains are vinylterminated. Other suitable catalysts may produce greater or fewernumbers of vinyl groups.

In one aspect of this invention, for ethylene homopolymers producedusing more than one catalyst in a single reactor, R_(v) is ≧0.14 foreach catalyst; preferably, R_(v) is ≧0.17; more preferably R_(v) is≧0.19; most preferably R_(v) is ≧0.21. For ethylene interpolymers havinga density of ≧0.920 g/mL produced using more than one catalyst in asingle reactor, R_(v) is ≧0.13 for each catalyst; preferably, R_(v) is≧0. 15, more preferably R_(v) is ≧0.17, most preferably R_(v) is ≧0.19.For ethylene interpolymers having a density greater than or equal to0.900 g/mL but less than 0.920 g/mL produced using more than onecatalyst in a single reactor, R_(v) is ≧0.12 for each catalyst;preferably, R_(v) is ≧0. 14; more preferably R_(v) is ≧0.16; mostpreferably R, is >0.18. For ethylene interpolymers having a densitygreater than or equal to 0.880 g/mL but less than 0.900 g/mL producedusing more than one catalyst in a single reactor, R_(v) is ≧0.10 foreach catalyst; preferably, R_(v) is ≧0.12; more preferably R, is >0.14;most preferably R_(v) is ≧0.16. For ethylene interpolymers having adensity less than 0.880 g/mL produced using more than one catalyst in asingle reactor, R_(v) is ≧0.08 for each catalyst; preferably, R_(v) is≧0.10; more preferably R_(v) is ≧0.12; most preferably R_(v) is ≧0.16.

In some embodiments of the invention, R_(v) for one or both of thecatalysts is substantially higher. Some catalysts have R_(v) values ofabout 0.25, about 0.30, about 0.35 or about 0.40. Other catalysts arecharacterized by an R_(v) of equal to or greater that about 0.50, about0.60, or about 0.75.

In some embodiments, the catalyst pairs are selected to givesubstantially equal amounts of long chain branching in the HMW componentand the LMW component. Thus, thee ratio R_(v) ^(L)/R_(v) ^(H) may begreater or less than 1. Preferably, the R_(v) ^(L)/R_(v) ^(H) ratioranges from 0.5 to about 2.0. In some embodiments, the R_(v) ^(L)/R_(v)^(H) ratio is about 0.60, 0.70, 0.80 or 0.90. In other embodiments, theratio is about 1.00, about 1.20, about 1.30 or about 1.40. In stillother embodiments, R_(v) ^(L)/R_(v) ^(H) is about 1.5, about 1.6, about1.7, about 1.8 or about 1.9. Catalyst pairs in which the low molecularweight catalyst has an R_(v) value that is higher than the R_(v) of thehigh molecular weight catalyst may be desirable for producing polymershaving increased branching in the LMW component of the polymercomposition.

Catalyst pairs may be selected by applying the following criteria. Thevinyl generation, comonomer incorporation, and relative molecular weightresponse is determined for each catalyst by analysis according toGeneral Procedure for Determining R_(v) and Comonomer Incorporation,described below. For the low molecular weight catalyst, a R_(v) greaterthan about 0.2, about 0.3, about 0.4 or about 0.5 is useful. The highmolecular weight catalyst is selected according to two criteria. First,the mole % 1-octene incorporation under the conditions of the testshould be greater than 2%, preferably greater than 2.5%. In someembodiments, the 1-octene incorporation may be greater than about 3.0%,greater than about 4.0%, or greater than 5.0%. The incorporation of longchain branches is generally better for catalysts that can incorporatehigher amounts of alpha olefins. The second criteria is based on themolecular weight of the polymer produced by the low molecular weightcatalyst. The high molecular weight catalyst should produce a polymerwith a M_(w), as determined by the experiment described in Example 20,greater than about two times the M_(w) of the polymer produced by the-low molecular weight catalyst.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. Alumoxane, when used by itself as an activatingcocatalyst, is generally employed in large quantity, generally at least100 times the quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane and tris(pentafluorophenyl) aluminum,where used as an activating cocatalyst are preferably employed in amolar ratio to the metal complex of from 0.5:1 to 10:1, more preferablyfrom 1:1 to 6:1 most preferably from 1:1 to 5:1. The remainingactivating cocatalysts are generally employed in approximately equimolarquantity with the metal complex.

In general, the polymerization may be accomplished at conditions knownin the art for Ziegler-Natta or Kaminsky-Sinn type polymerizationreactions, that is, temperatures from −50 to 250° C., preferably 30 to200° C. and pressures from atmospheric to 10,000 atmospheres.Suspension, solution, slurry, gas phase, solid state powderpolymerization or other process condition may be employed if desired. Asupport, especially silica, alumina, or a polymer (especiallypolytetrafluoroethylene or a polyolefin) may be employed, and desirablyis employed when the catalysts are used in a gas phase or slurrypolymerization process. Preferably, the support is passivated before theaddition of the catalyst. Passivation techniques are known in the art,and include treatment of the support with a passivating agent such astriethylaluminum. The support is preferably employed in an amount toprovide a weight ratio of catalyst (based on metal):support from about1:100,000 to about 1:10, more preferably from about 1:50,000 to about1:20, and most preferably from about 1:10,000 to about 1:30. In mostpolymerization reactions, the molar ratio of catalyst:polymerizablecompounds employed preferably is from about 10⁻¹²:1 to about 10⁻¹:1,more preferably from about 10⁻⁹:1 to about 10⁻⁵:1.

Suitable solvents for polymerization are inert liquids. Examplesinclude, but are not limited to, straight and branched-chainhydrocarbons such as isobutane, butane, pentane, hexane, heptane,octane, and mixtures thereof; mixed aliphatic hydrocarbon solvents suchas kerosene and ISOPAR (available from Exxon Chemicals), cyclic andalicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof;perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀ alkanes, andthe like, and aromatic and alkyl-substituted aromatic compounds such asbenzene, toluene, xylene, ethylbenzene and the like. Suitable solventsalso include, but are not limited to, liquid olefins which may act asmonomers or comonomers including ethylene, propylene, butadiene,cyclopentene, 1-hexene, 1-hexane, 4-vinylcyclohexene, vinylcyclohexane,3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene,1-decene, styrene, divinylbenzene, allylbenzene, vinyltoluene (includingall isomers alone or in admixture), and the like. Mixtures of theforegoing are also suitable.

The catalysts may be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst inseparate reactors connected in series or in parallel to prepare polymerblends having desirable properties. An example of such a process isdisclosed in WO 94/00500, equivalent to U.S. Ser. No. 07/904,770, aswell as U.S. Ser. No. 08/10958, filed Jan. 29, 1993. The disclosures ofthe patent applications are incorporated by references herein in theirentirety.

The catalyst system may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent in whichpolymerization will be carried out by solution polymerizationprocedures. The catalyst system may also be prepared and employed as aheterogeneous catalyst by adsorbing therequisite components on acatalyst support material such as silica gel, alumina or other suitableinorganic support material. When prepared in heterogeneous or supportedform, it is preferred to use silica as the support material. Theheterogeneous form of the catalyst system may be employed in a slurrypolymerization. As a practical limitation, slurry polymerization takesplace in liquid diluents in which the polymer product is substantiallyinsoluble. Preferably, the diluent for slurry polymerization is one ormore hydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orin part as the diluent. Likewise the α-olefin monomer or a mixture ofdifferent α-olefin monomers may be used in whole or part as the diluent.Most preferably, the major part of the diluent comprises at least theα-olefin monomer or monomers to be polymerized.

Solution polymerization conditions utilize a solvent for the respectivecomponents of the reaction. Preferred solvents include, but are notlimited to, mineral oils and the various hydrocarbons which are liquidat reaction temperatures and pressures. Illustrative examples of usefulsolvents include, but are not limited to, alkanes such as pentane,isopentane, hexane, heptane, octane and nonane, as well as mixtures ofalkanes including kerosene and Isopar Em™, available from ExxonChemicals Inc.; cycloalkanes such as cyclopentane, cyclohexane, andmethylcyclohexane; and aromatics such as benzene, toluene, xylenes,ethylbenzene and diethylbenzene.

The polymerization may be carried out as a batch or a continuouspolymerization process. A continuous process is preferred, in whichevent catalysts, solvent or diluent (if employed), and comonomers (ormonomer) are continuously supplied to the reaction zone and polymerproduct continuously removed therefrom. The polymerization conditionsfor manufacturing the interpolymers according to embodiments of theinvention are generally those useful in the solution polymerizationprocess, although the application is not limited thereto. Gas phase andslurry polymerization processes are also believed to be useful, providedthe proper catalysts and polymerization conditions are employed.

In some embodiments, the polymerization is conducted in a continuoussolution polymerization system comprising two reactors connected inseries or parallel. One or both reactors contain at least two catalystswhich have a substantially similar comonomer incorporation capabilitybut different molecular weight capability. In one reactor, a relativelyhigh molecular weight product (M_(w) from 100,000 to over 1,000,000,more preferably 200,000 to 1,000,000) is formed while in the secondreactor a product of a relatively low molecular weight (M2,000 to300,000) is formed. The final product is a mixture of the reactoreffluents which are combined prior to devolatilization to result in auniform mixing of the two polymer products. Such a dual reactor/dualcatalyst process allows for the preparation of products with tailoredproperties. In one embodiment, the reactors are connected in series,that is the effluent from the first reactor is charged to the secondreactor and fresh monomer, solvent and hydrogen is added to the secondreactor. Reactor conditions are adjusted such that the weight ratio ofpolymer produced in the first reactor to that produced in the secondreactor is from 20:80 to 80:20. In addition, the temperature of thesecond reactor is controlled to produce the lower molecular weightproduct In one embodiment, the second reactor in a series polymerizationprocess contains a heterogeneous Ziegler-Natta catalyst or chromecatalyst known in the art. Examples of Ziegler-Natta catalysts include,but are not limited to, titanium-based catalysts supported on MgCl₂, andadditionally comprise compounds of aluminum containing at least onealuminumalkyl bond. Suitable Ziegler-Natta catalysts and theirpreparation include, but are not limited to, those disclosed in U.S.Pat. Nos. 4,612,300, 4,330,646, and 5,869,575. The disclosures of eachof these three patents are herein incorporated by reference.

In some embodiments, ethylene is added to the reaction vessel in anamount to maintain a differential pressure in excess of the combinedvapor pressure of the α-olefin and diene monomers. The ethylene contentof the polymer is determined by the ratio of ethylene differentialpressure to the total reactor pressure. Generally the polymerizationprocess is carried outwith a pressure of ethylene of from 10 to 1000 psi(70 to 7000 kPa), most preferably from 40 to 800 psi (30 to 600 kPa).The polymerization is generally conducted at a temperature of from 25 to250° C., preferably from 75 to 200° C., and most preferably from greaterthan 95 to 200° C.

The optional cocatalysts and scavenger components in the novel processcan be independently mixed with each catalyst component before thecatalyst components are introduced into the reactor, or they may eachindependently be fed into the reactor using separate streams, resultingin “in reactor” activation. Scavenger components are known in the artand include, but are not limited to, alkyl aluminum compounds, includingalumoxanes. Examples of scavengers include, but are not limited to,trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctylaluminum, methylalumoxane (MAO), and other alumoxanes including, but notlimited to, MMAO-3A, MMAO-7, PMAO-IP (all available from Akzo Nobel).

For the novel processes described herein, the polymer properties can betailored by adjustment of process conditions. Process conditionsgenerally refer to temperature, pressure, monomer content (includingcomonomer concentration), catalyst concentration, cocatalystconcentration, activator concentration, etc., that influence themolecular weight or branching of the polymer produced. In general, forethylene based polymers, the amount of long chain branching increaseswith a decrease in the concentration of ethylene. Thus, particularly insolution polymerization, the amount of long-chain branching can becontrolled by adjusting the ethylene concentration, reactor temperature,and polymer concentration. In general, higher reactor temperatures leadto a higher level of polymer molecules that have unsaturated end groups.Long chain branching can be increased by selecting catalysts thatgenerate a relatively large percentage of vinyl end groups, selectingcatalysts having relatively high comonomer incorporating ability (i.e.,low r₁), operating at relatively high reactor temperature at lowethylene and comonomer concentration, and high polymer concentration. Byproper selection of process conditions, including catalyst selection,polymers with tailored properties can be produced. For a solutionpolymerization process, especially a continuous solution polymerization,preferred ranges of ethylene concentration at steady state are fromabout 0.25 weight percent of the total reactor contents to about 5weight percent of the total reactor contents, and the preferred range ofpolymer concentration is from about 10% of the reactor contents byweight to about 45% of the reactor contents or higher.

Applications:

The polymers made in accordance with embodiments of the invention havemany useful applications. For example, fabricated articles made from thepolymers may be prepared using all of the conventional polyolefinprocessing techniques. Useful articles include films (e.g., cast, blownand extrusion coated), including multi-layer films, fibers (e.g., staplefibers) including use of an interpolymer disclosed herein as at leastone component comprising at least a portion of the fiber's surface,spunbond fibers or melt blown fibers (using, e.g., systems as disclosedin U.S. Pat No. 4,430,563, U.S. Pat. No. 4,663,220, U.S. Pat. No.4,668,566, or U.S. Pat. No. 4,322,027, all of which are incorporatedherein by reference), and gel spun fibers (e.g., the system disclosed inU.S. Pat. No. 4,413,110, incorporated herein by reference), both wovenand nonwoven fabrics (e.g., spunlaced fabrics disclosed in U.S. Pat. No.3,485,706, incorporated herein by reference) or structures made fromsuch fibers (including, e.g., blends of these fibers with other fibers,e.g., PET or cotton) and molded articles (e.g., made using an injectionmolding process, a blow molding process or a rotomolding process).Monolayer and multilayer films may be made according to the filmstructures and fabrication methods described in U.S. Pat. No. 5,685,128,which is incorporated by reference herein in its entirety. The polymersdescribed herein are also useful for wire and cable coating operations,as well as in sheet extrusion for vacuum forming operations.

Specific applications wherein the inventive polymers disclosed hereinmay be used include, but are not limited to, greenhouse films, shrinkfilm, clarity shrink film, lamination film, extrusion coating, liners,clarity liners, overwrap film, agricultural film, high strength foam,soft foam, rigid foam, cross-linked foam, high strength foam forcushioning applications, sound insulation foam, blow molded bottles,wire and cable jacketing, including medium and high voltage cablejacketing, wire and cable insulation, especially medium and high voltagecable insulation, telecommunications cable jackets, optical fiberjackets, pipes, and frozen food packages. Some such uses are disclosedin U.S. Pat. No. 6,325,956, incorporated here by reference in itsentirety. Additionally, the polymers disclosed herein may replace one ormore of those used in the compositions and structures described in U.S.Pat. No. 6,270,856, U.S. Pat. No. 5,674,613, U.S. Pat. No. 5,462,807,U.S. Pat. No. 5,246,783,. and U.S. Pat. No. 4,508,771, each of which isincorporated herein by reference in it entirety. The skilled artisanwill appreciate other uses for the novel polymers and compositionsdisclosed herein.

Useful compositions are also suitably prepared comprising the polymersaccording to embodiments of the invention and at least one other naturalor synthetic polymer. Preferred other polymers include, but are notlimited to, thernoplastics, such as styrene-butadiene block copolymers,polystyrene (including high impact polystyrene), ethylene vinyl alcoholcopolymers, ethylene vinyl acetate copolymers, ethylene acrylic acidcopolymers, other olefin copolymers (especially polyethylenecopolymers).and homopolymers (e.g., those made using conventionalheterogeneous catalysts). Examples include polymers made by the processof U.S. Pat. No. 4,076,698, incorporated herein by reference, otherlinear or substantially linear polymers as described in U.S. Pat. No.5,272,236, and mixtures thereof. Other substantially linear polymers andconventional HDPE and/or LDPE may also be used in the thermoplasticcompositions.

EXAMPLES

The following examples are given to illustrate various embodiments ofthe invention. They do not intend to limit the invention as otherwisedescribed and claimed herein. All numerical values are approximate. Whena numerical range is given, it should be understood that embodimentsoutside the range are still within the scope of the invention unlessotherwise indicated. In the following examples, various polymers werecharacterized by a number of methods. Performance data of these polymerswere also obtained. Most of the methods or tests were performed inaccordance with an ASTM standard, if applicable, or known procedures.

Unless indicated otherwise, the following testing procedures are to beemployed:

Density is measured in accordance with ASTM D-792. The samples areannealed at ambient conditions for 24 hours before the measurement istaken.

The molecular weight of polyolefin polymers is conveniently indicatedusing a melt index measurement according to ASTM D-1238, Condition 190°C./2.16 kg (formerly known as “Condition E” and also known as I₂). Meltindex is inversely proportional to the molecular weight of the polymer.Thus, the higher the molecular weight, the lower the melt index,although the relationship is not linear. The overall I₂ melt index ofthe novel composition is in the range of from 0.01 to 1000 g/10 minutes.Other measurements useful in characterizing the molecular weight ofethylene interpolymer compositions involve melt index determinationswith higher weights, such as, for common example, ASTM D-1238, Condition190° C./10 kg (formerly known as “Condition N” and also known as Ilo).The ratio of a higher weight melt index determination to a lower weightdetermination is known as a melt flow ratio, and for measured I₁₀ andthe I₂ melt index values the melt flow ratio is conveniently designatedas I₁₀/I₂.

Gel Permeation Chromatography (GPC) data were generated using either aWaters 150C/ALC, a Polymer Laboratories Model PL-210 or a PolymerLaboratories Model PL-220. The column and carousel compartments wereoperated at 140 ° C. The columns used were 3 Polymer Laboratories 10micron Mixed-B columns. The samples were prepared at a concentration of0.1 grams of polymer in 50 milliliters of 1,2,4 trichlorobenzene. The1,2,4 trichlorobenzene used to prepare the samples contained 200 ppm ofbutylated hydroxytoluene (BHT). Samples were prepared by agitatinglightly for 2 hours at 160° C. The injection volume used was 100microliters and the flow rate was 1.0 milliliters/minute. Calibration ofthe GPC was performed with narrow molecular weight distributionpolystyrene standards purchased from Polymer Laboratories. Thesepolystyrene standard peak molecular weights were converted topolyethylene molecular weights using the following equation (asdescribed in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621(1968):M _(polyethylene) =A×(M _(polystyrene))^(B)where M is the molecular weight, A has a value of 0.4316 and B is equalto 1.0. The molecular weight calculations were performed with theViscotek TriSEC software.

The GPC data were then deconvoluted to give the most probable fit fortwo molecular weight components. There are a number of deconvolutionalgorithms available both commercially and in the literature. These maylead to different answers depending upon the assumptions used. Thealgorithm summarized here is optimized for the deconvolution problem ofthe two most probable molecular weight distributions (plus an adjustableerror term). In order to allow for the variations in the underlyingdistributions due to the macromer incorporation and small fluctuationsin the reactor conditions (i.e. temperature, concentration) the basisfunctions were modified to incorporate a normal distribution term. Thisterm allows the basis function for each component to be “smeared” tovarying degrees along the molecular weight axis. The advantage is thatin the limit (low LCB, perfect concentration and temperature control)the basis function will become a simple, most probable, Florydistribution.

Three components (j=1,2,3) are derived with the third component (j=3)being an adjustable error term. The GPC data must be normalized andproperly transformed into weight fraction versus Log₁₀ molecular weightvectors. In other words, each potential curve for deconvolution shouldconsist of a height vector, h_(i), where the heights are reported atknown intervals of Log₁₀ molecular weight, the h_(i) have been properlytransformed from the elution volume domain to the Log₁₀ molecular weightdomain, and the h_(i) are normalized. Additionally, these data should bemade available for the Microsoft EXCEL™ application.

Several assumption are made in the deconvolution. Each component, j,consists of a most probable, Flory, distribution which has beenconvoluted with a normal or Gaussian spreading function using aparameter, σ_(j). The resulting, three basis finctions are used in aChi-square, X², minimization routine to locate the parameters that bestfit the n points in h_(i), the GPC data vector. $\begin{matrix}{{X^{2}\left( {\mu_{j},\sigma_{j},w_{j}} \right)} = {\sum\limits_{i = 1}^{n}\left\lbrack {\sum\limits_{j = 1}^{3}{\cdot {\sum\limits_{k = 1}^{20}{w_{j} \cdot M_{i}^{2} \cdot \lambda_{j,k}^{2} \cdot {CumND}_{j,k} \cdot}}}} \right.}} \\\left. {{{{\mathbb{e}}^{{- \lambda_{j,k}} \cdot M_{i}} \cdot \Delta}\quad{Log}_{10}M} - h_{i}} \right\rbrack^{2}\end{matrix}$$\lambda_{j,k} = 10^{\mu_{j} + {\frac{k - 10}{3} \cdot \sigma_{j}}}$The variable, CumND_(j,k), is calculated using the EXCEL™ function“NORMDIST(x, mean, standard_dev, cumulative)” with the parameters set asfollows:x=μ _(j)+(k−10)* σ_(j)/3mean=μ_(j)standard dev=σ_(j)cumulative=TRUE

Table I below summarizes these variables and their definitions. The useof the EXCEL™ software application, Solver, is adequate for this task.Constraints are added to Solver insure proper minimzation. TABLE IVariable Definitions Variable Name Definition λ_(j,k) Reciprocal of thenumber average molecular weight of most probable (Flory) distributionfor component j, normal distribution slice k σ_(j) Sigma (square root ofvariance) for normal (Gaussian) spreading function for component j.w_(j) Weight fraction of component j K Normalization term (1.0/Log_(e)10) M_(i) Molecular weight at elution volume slice i h_(i) Height oflog₁₀ (molecular weight) plot at slice i n Number of slices in Logmolecular weight plot i Log molecular weight slice index (1 to n) jComponent index (1 to 3) l. k Normal distribution slice index Δlog₁₀MAverage difference between log₁₀M_(i) and log₁₀M_(i−1)in height vs.log₁₀M plot

The 8 parameters that are derived from the Chi-square minimization areμ₁, μ₂, μ₃, σ₁, σ₂, σ₃, w₁, and w₂. The term w₃ is subsequently derivedfrom w₁ and W₂ since the sum of the 3 components must equal 1. Table IIis a summary of the Solver constraints used in the EXCEL program. TABLEII Constraint summary Description Constraint Maximum of fraction 1 w₁ <0.95 (User adjustable) Lower limit of spreading function σ₁, σ₂, σ₃ >0.001 (must be positive) Upper limit of spreading function σ₁, σ₂, σ₃ <0.2 (User adjustable) Normalized fractions w₁ + w₂ + w₃ = 1.0

Additional constraints that are to be understood include the limitationthat only μ_(j)>0 are allowed, although if solver is properlyinitialized, this constraint need not be entered, as the solver routinewill not move any of the μ_(j) to values less than about 0.005. Also,the w_(j) are all understood to be positive. This constraint can behandled outside of solver. If the w_(j) are understood to arise from theselection of two points along the interval 0.0<P₁<P₂<1.0; whereby w₁=P₁,w₂=P₂−P₁ and w₃=1.0−P₂; then constraining P1 and P2 are equivalent tothe constraints required above for the w_(j).

Table III is a summary of the Solver settings under the Options tab.TABLE III Solver settings Label Value or selection Max Time (seconds)1000 Iterations 100 Precision 0.000001 Tolerance (%) 5 Convergence 0.001Estimates Tangent Derivatives Forward Search Newton ALL OTHER SELECTIONSNot selected

A first guess for the values of μ₁, μ₂, w₁, and w₂ can be obtained byassuming two ideal Flory components that give the observed weightaverage, number average, and z-average molecular weights for theobserved GPC distribution.$M_{n,{GPC}} = \left\lbrack {{w_{1} \cdot \frac{1}{10^{\mu_{1}}}} + {w_{2} \cdot \frac{1}{10^{\mu_{2}}}}} \right\rbrack^{- 1}$$M_{w,{GPC}} = \frac{\left\lbrack {{w_{1} \cdot 2 \cdot 10^{\mu_{1}}} + {w_{2} \cdot 2 \cdot 10^{\mu_{2}}}} \right\rbrack}{M_{n,{GPC}}}$$M_{z,{GPC}} = \frac{\left\lbrack {{w_{1} \cdot 6 \cdot 10^{\mu_{1}}} + {w_{2} \cdot 6 \cdot 10^{\mu_{2}}}} \right\rbrack}{M_{w,{GPC}}}$w₁ + w₂ = 1The values of μ₁, μ₂, w₁, and w₂ are then calculated. These should beadjusted carefully to allow for a small error term, w₃, and to meet theconstraints in Table II before entering into Solver for the minimizationstep. Starting values for σ_(j) are all set to 0.05.

Preparative GPC for collecting selected fractions of polymers wasperformed on a Waters 150C/ALC equipped with preparative pump heads andmodified with a 3000 microliter injection loop and 14 milliliter samplevials. The column and carousel compartments were operated at 140° C. Thepreparative GPC column used was 1 Jordi Associaties 5 microndivinylbenzene (DVB) column catalog number 15105. The column dimensionswere 500 mm in length and 22 mm inner diameter. 1,2,4 trichlorobenzenewas used for both sample preparation and as the chromatographic mobilephase. The samples were prepared at a concentration of 0.1 grams ofpolymer in 50 milliliters of solvent. The solvent used to prepare thesamples contained 200 ppm of butylated hydroxytoluene (BHT). Sampleswere prepared by agitating lightly for 2 hours at 160° C. The injectionvolume used was 2,500 microliters and the flow rate was 5.0milliliters/minute.

Approximately 200-300 injections were made to collect appropriate sampleamounts for off-line analysis. 16 fractions were collected spanning thefull column elution range, with 8-12 fractions typically spanning thesample elution range. Elution range was verified by refractive indexanalysis during start-up. The collected solvent fractions wereevaporated to approximately 50-60 milliliter volumes with a BuchiRotovapor R-205 unit equipped with a vacuum controller module V-805 anda heating bath module B-409. The fractions were then allowed to cool toroom temperature and the polyethylene material was precipitated byadding approximately 200 milliliters of methanol. Verification ofmolecular weight fractionation was done via high temperature GPCanalysis with refractive index detection. Typical polydispersities ofthe fractions as measured by GPC analysis were approximately 1.1 to 1.4.

The weight average branching index for selected fractions was obtainedfrom direct determination of intrinsic viscosity and molecular weight ateach chromatographic data slice. The chromatographic system consisted ofeither a Polymer Laboratories Model PL-210 or a Polymer LaboratoriesModel PL-220 equipped with a Viscotek differential viscometer Model210R, and a Precision Detectors 2-angle laser light scattering detectorModel 2040. The 15-degree angle of the light scattering detector wasused for the calculation of molecular weights.

The column and carousel compartments were operated at 140° C. Thecolumns used were 3 Polymer Laboratories 10-micron Mixed-B columns. Thesolvent used was 1,2,4 trichlorobenzene. The samples were prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solvent. Thesolvent used to prepare the samples contained 200 ppm of butylatedhydroxytoluene (BHT). Samples were prepared by agitating lightly for 2hours at 160° C. The injection volume used was 100 microliters and theflow rate was 1.0 milliliters/minute.

Calibration of the GPC column set was performed with narrow molecularweight distribution polystyrene standards purchased from PolymerLaboratories. The calibration of the detectors was performed in a mannertraceable to NBS 1475 using a linear polyethylene homopolymer. ¹³C NMRwas used to verify the linearity and composition of the homopolymerstandard. The refractometer was calibrated for mass verificationpurposes based on the known concentration and injection volume. Theviscoimeter was calibrated with NBS 1475 using a value of 1.01deciliters/gram and the light scattering detector was calibrated usingNBS 1475 using a molecular weight of 52,000 Daltons.

The Systematic Approach for the determination of multi-detector offsetswas done in a manner consistent with that published by Mourey and Balke,Chromatography of Polymers: T. Provder, Ed.; ACS Symposium Series 521;American Chemical Society: Washington, D.C., (1993) pp 180-198 andBalke, et al.,; T. Provder, Ed.; ACS Symposium Series 521; AmericanChemical Society: Washington, D.C., (1993): pp 199-219., both of whichare incorporated herein by reference in their entirety. The tripledetector results were compared with polystyrene standard referencematerial NBS 706 (National Bureau of Standards), or DOW chemicalpolystyrene resin 1683 to the polystyrene column calibration resultsfrom the polystyrene narrow standards calibration curve.

Verification of detector alignment and calibration was made by analyzinga linear polyethylene homopolymer with a polydispersity of approximately3 and a molecular weight of 115,000. The slope of the resultantMark-Houwink plot of the linear homopolymer was verified to be withinthe range of 0.725 to 0.730 between 30,000 and 600,000 molecular weight.The verification procedure included analyzing a minimum of 3 injectionsto ensure reliability. The polystyrene standard peak molecular weightswere converted to polyethylene molecular weights using the method ofWilliams and Ward described previously. The agreement for M_(w) andM_(n) between the polystyrene calibration method and the absolute tripledetector method were verified to be within 5% for the polyethylenehomopolymer.

The intrinsic viscosity data was obtained in a manner consistent withthe Haney 4-capillary viscometer described in U.S. Pat. No. 4,463,598,incorporated herein by reference. The molecular weight data was obtainedin a manner consistent with that published by Zimm (Zimm, B. H., J.Chem.Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical LightScattering from Polymer Solutions, Elsevier, Oxford, N.Y. (1987)). Theoverall injected concentration used for the determination of theintrinsic viscosity and molecular weight were obtained from the samplerefractive index area and the refractive index detector calibration fromthe linear polyethylene homopolymer and all samples were found to bewithin experimental error of the nominal concentration. Thechromatographic concentrations were assumed low enough to liminate theneed for a Huggin's constant (concentration effects on intrinsicviscosity) and second virial coefficient effects (concentration effectson molecular weight).

For samples that contain comonomer, the measured g′ represents effectsof both long chain branching as well as short chain branching due tocomonomer. For samples that have copolymer component(s), thecontribution from short chain branching structure should be removed astaught in Scholte et al., discussed above. If the comonomer isincorporated in such a manner that the short chain branching structureis proven both equivalent and constant across both the low and highmolecular weight components, then. the difference in long chainbranching index between 100,000 and 500,000 may be directly calculatedfrom the copolymer sample. For cases where the comonomer incorporationcannot be proven both equivalent and constant across both the high andlow molecular weight components, then preparative GPC fractionation isrequired in order to isolate narrow molecular weight fractions withpolydispersity lower than 1.4. ¹³C NMR is used to determine thecomonomer content of the preparative fractions.

Additionally, a calibration of g′ against comonomer type for a series oflinear copolymers of the same comonomer is established in order tocorrect for comonomer content, in cases where comonomer incorporationcannot be shown to be both equivalent and constant across both the highand low molecular weight components. The g′ value is then analyzed forthe isolated fraction corresponding to the desired molecular weightregion of interest and corrected via the comonomer calibration functionto remove comonomer effects. from g′. Estimation of number of branchesper molecule on the high Molecular weight species.

The number of long chain branches per molecule was also determined byGPC methods. High temperature GPC results (HTGPC) were compared withhigh temperature GPC light scattering results (HTGPC-LS). Suchmeasurements can be conveniently recorded on a calibrated GPC systemcontaining both light scattering and concentrations detectors whichallows the necessary data to be collected from a single chromatographicsystem and injection. These measurements assume that the separationmechanism by HTGPC is due to the longest contiguous backbone segmentthrough a polymer molecule (i.e. the backbone). Therefore, it. assumesthat the molecular weight obtained by HTGPC produces the backbonemolecular weight (linear equivalent molecular weight) of the polymer.The average sum of the molecular weight of long chain branches added tothe backbone at any chromatographic data slice is obtained bysubtracting the backbone molecular weight estimatefrom the absolutemolecular weight obtained by HTGPC-LS. If there is a significantcomonomer content differential between the high and low molecular weightspecies in the polymer, it is necessary to subtract the weight of thecomonomer from the HTGPC-LS results using knowledge of the highmolecular weight catalyst.

The average molecular weight of the long chain branches that are addedto the high molecular weight polymer is assumed to be equivalent to thenumber-average molecular weight of the bulk polymer (considering bothhigh and low molecular weight species). Alternatively, an estimate ofthe average molecular weight of a long chain branch can be obtained bydividing the weight-average molecular weight of the low molecular weightspecies (obtained through de-convolution techniques) by a polydispersityestimate of the low molecular weight species. If there is a significantcomonomer content differential between the high and low molecular weightspecies in the polymer, it is necessary to add or subtract thedifferential total weight of comonomer from the number average molecularweight results first using knowledge of the comonomer incorporation forthe low molecular weight catalyst.

The number of long chain branches at any chromatographic slice isestimated by dividing the sum of the molecular weight of the total longchain branches by the average molecular weight of the long chain branch.By averaging this number of long chain branches weighted by thedeconvoluted high molecular weight peak, the average amount of longchain branching for the high molecular weight species is determined.Although assumptions are made in regard to GPC separation and the factthat the polymer backbone can be extended due to a long chain branchincorporating near to the chain ends of the backbone segment, we havefound this measure of number of branches to be very useful in predictingresin performance.

Melt strength measurements were conducted on a Goettfert Rheotens 71.97attached to an Model 3211 Instron capillary rheometer. A polymer meltwas extruded through a capillary die (flat die, 180 degree angle) with acapillary diameter of 2.1 mm and an aspect ratio (capillarylength/capillary radius) of 20 with an entrance angle of approximately45 degrees at a constant plunger velocity. After equilibrating thesamples at 190° C. for 10 minutes, the piston is run at a speed of 1inch/minute (2.54 cm/min). The standard test temperature is 19.° C. thesample is drawn uniaxially to a set of accelerating nips located 100 mmbelow the die with an acceleration of 2.4 mm/s². The tensile force isrecorded as a finction of the take-up speed of the nip rolls. Meltstrength was reported as the plateauforce (cN) before the strand broke.The following conditions were used in the melt strength measurements.plunger speed=0.423 mm/swheel acceleration 32 2.4 mm/s/scapillary diameter=2.1 mmcapillary length=42 mmbarrel diameter=9.52 mmSynthesis of(N-(1,1-dimethylethyl)-1,1-di-(4-n-butyl-iohenyl)-1-((1,2,3,a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-C-yl)silanaminato-(2-)-N-)dimethyltitanium(Catalyst A)(1) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di(4-butyl-phenyl)-1-((1,2,3,3a,7a-η)3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium

[A] Synthesis ofdichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-n)3(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato(2)N-)titanium

(i) Preparation of (p-Bu-Ph)₂SiCl₂.

To a three-necked 250 mL round-bottom flask under a nitrogen atmosphereequipped with a reflux condenser and a 250 mL dropping funnel 4.87g ofMg turnings (0.200 moles) were introduced 1-bromo4-butyl benzene(42.62g, 0.200 moles) and 80 mL of THF were then added to the droppingfimnel. At this time 10 mL of the bromobenzene/TBF solution was added tothe Mg turnigs with a small amount of ethyl bromnide. The solution wasthen stirred until initiation occurred. The rest of the bromobenzene/THF solution was then added dropwise to allow refluxing tooccur. After addition of the bromo benzne/THF solution, the mixture washeated at reflux until the magnesium was consumed.

The resulting Grignard solution was then transferred to a 250 mLdropping funnel which was attached to a three-necked 250 mL round-bottomflask under a nitrogen atmosphere equipped with a reflux condenser. Tothe round bottomed flask 100 mL of heptane was introduced followed bySiCl₄ (15.29 g, 0.090 moles). To this solution, the Grignard solutionwas added dropwise. After addition was complete the resulting mixturewas refluxed for 2 h and then allowed to cool to room temperature. Underan inert atmosphere the solution was filtered. The remaining salts werefurther washed with heptane (3×40 mL), the washings were combined withthe original heptane solution.

The heptane was then removed via distillation at atmospheric pressure.The resulting viscous oil was then vacuumed distilled with collection ofthe product at 1 mm at 210° C. giving 19.3 g (58%). ¹H (C₆D₆) δ: 0.80(t, 6H), 1.19 (m, 4 H), 1.39 (m, 4 H), 2.35 (t, 4 H), 7.0 (d, 4 H), 7.7(d, 4H).(ii) Preparation of (pBu-Ph)₂Si(Cl)(NH-t-Bu).

Dichloro-di(p-butylpheny)silane (4.572 gg 12.51 mmol) was dissolved in45 mL of methylene chloride. To this solution was added 1.83 g, 25.03mmol of t-BuNH₂. After stirring overnight Solvent was removed underreduced pressure. The residue was extracted with 45 nL of hexane andfiltered. Solvent was removed under reduced pressure leaving 4.852 g ofproduct as an off-white oil. ¹H (C₆D₆) δ: 0.75 (t, 6 H), 1.15 (s, 9 H),1.2 (m, 4 H), 1.4 (m, 4 H), 1.51 (s, 1 H), 2.4 (t, 4 H), 7.05 (d, 4 H),7.8 (d, 4 H).(iii) Preparation of (pBu-Ph)₂Si(3-isoindolino-indenyl)(NH-t-Bu).

To a 4.612 g (11.47 mmol) of (p-Bu-Ph)₂Si(Cl)(NH-t-Bu) dissolved in 20mL of THF was added 2.744 g (8.37 mmol) of lithium1-isoindolino-indenide dissolved in 30 mL of THF. After the reactionmixture was stirred overnight, solvent was removed under reducedpressure. The residue was extracted with 5 mL of hexane and filtered.Solvent removal gave 6.870 g of product as very viscous red-brown oil.Yield 91.0% ¹H (C₆D₆) 8:0.75 (m, 6 H), 1.15 (s, 9 H), 1.25 (mn, 4 H),2.4 (m, 4H), 4.2 (s, 1H), 4.5 (dd, 4 H), 5.6 (s, 1H)6.9 - 7.7 (m, 16,H).

[B] Preparation of Dilithium Salt of(pBu-Ph)2Si(3-isoindolino-indenyl)(NH-t-Bu).

To a 50 mL of hexane solution containing 6.186 g (10.33 mmol) of(p-Bu-Ph)₂Si(3-isoindolino-indenyl)(NH-t-Bu) was added 13.5 mL of 1.6 Mn-BuLi solution. A few minutes after n-BuLi addition a yellowprecipitate appeared. After stiring overnight the yellow precipitate wascollected on the frit, washed with 4×20 mL of hexane and dried underreduced pressure to give 4.4181 g of product as yellow powder. Yield70.0%.[C] Preparation ofdichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-n)3(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2)-N-)titanium.

In the drybox 2.620 g (7.1 mmol) of TiCl₃(F)₃ was suspended in 40 mL ofTHF. To this solution 4.319 g (7.07 mmol) of dilithium salt of(p-Bu-Ph)₂Si(3-isoindolinoindenyl)(NH-t-Bu) dissolved in 60 mL of THFwas added within 2 min. The solution was then stirred for 60 min. Afterthis time 1.278 g of PbCl₂ (4.60 mmol) was added and the solution wasstirred for 60 min. The THF was then removed under reduced pressure. Theresidue was extracted with 50 mL of toluene and filtered. Solvent wasremoved under reduced pressure leaving black crystalline solid. Hexanewas added (35 mL) and the black suspension was stirred for 0.5 hr. Solidwas collected on the frit, washed with 2×30 mL of hexane and dried underreduced pressure to give 4.6754 g of product as black-blue crystallinesolid. Yield 92.4%o. ¹H (toluene-d4) δ: 0.75 (m, 6 H), 1.25 (m, 4 H),1.5 (m, 4 H), 1.65 (s, 9 H), 2.5 (t, 4 H), 4.5 (d, 2 H), 5.0 (d, 2 H),6.0 (s, 1 H), 6.8-8.2 (m, 16 H).(2) Preparation of(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-n)3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato(2-)N-)dimethyltitanium.

Thedichloro(N-1,1-dimethylethyl)-1,1-(4-butyl-phenyl)-1-((1,2,3,3a,7a-n)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium(1.608 g, 2.25 mmol) was suspended in 35 mL of toluene. To this solutionwas added 3 mL (4.75 mmol) of 1.6 M MeLi ether solution. Reaction colorchanged at once from dark green-black to dark red. After stiring for 1hr solvent was removed under reduced pressure. The residue was extractedwith 55 mL of hexane and filtered. Solvent was removed leaving 1.456 gof red solid. Yield 96%. ¹H (toluene-d₈) δ:0.3 (s, 3 H), 0.8 (m, 6 H),1.05 (s, 3 H), 1.25 (m, 4 H), 1.5 (m, 4 H), 1.75 (s, 9 H), 2.5 (m, 4 H),4.5 (d, 2 H), 4.8 (d, 2 H), 5.7 (s, 1 H), 6.7-8.3 (m, 16 H).

Synthesis of rac-[1,2-ethanediylbis(1-indenyl)]zirconium(1,4-diphenyl-1,3-butadiene) (Catalyst B)

Catalyst B can be synthesized according to Example 11 of U.S. Pat. No.5,616,664, the entire disclosure of which patent is incorporated hereinby reference.

Synthesis of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) (Catalyst C)

Catalyst C can be synthesized according to Example 17 of U.S. Pat. No.5,556,928, the entire disclosure of which patent is incorporated hereinby reference.

Synthesis of dimethylsilyl(2-methyl-s-indacenyl)(t-butylamido) titanium1,3-penitadiene (Catalyst D)

Catalyst D can be synthesized according to Example 23 of U.S. Pat. No.5,965,756, the entire disclosure of which patent is incorporated hereinby reference.

Synthesis of [(3-Phenylindenyl)SiMe₂N^(t)But]TiMe₂ (Catalyst E)

Catalyst F can be synthesized according to Example 2 of U.S. Pat. No.5,866,704, the entire disclosure of which patent is incorporated hereinby reference.

Synthesis ofdimethylamidoborane-bis-η⁵-(2-methyl-4nathythlinden-1-yl)zirconiumη⁴-1,4diphenyl-1,3-butadiene (Catalyst F)

Catalyst G can be synthesized according to Example 12 of WO 0020426, theentire disclosure of which patent is incorporated herein by reference.

Synthesis of(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((12,3,3a,9a,-h)5,6,7,8-tetrahydro-3-phenyl-5,5,8,8-tetramethyl-1H-benz(f)inden-1-yl)silanaminato(2-)N)dimethyltitanium (Catalyst G)

Catalyst H can be synthesized according to Example 13 of WO 9827103, theentire disclosure of which patent is incorporated herein by reference.

Synthesis of bis(n-butylcycloventadienyl)zirconium dimethyl (Catalyst H)

Bis(n-butylcyclopentadienylzirconium dichloride can be purchased fromBoulder Scientific. In a drybox, 12.00 g ofbis(n-butylcyclopentadienyizirconium dichloride was dissolved in 100 mLof diethyl ether in an 8 oz jar. 20.765 mL of 3.0 M methyl magnesiumchloride in THF (available from Aldrich Chemical Company) was addeddropwise via syringe with stirTing. After stining for 30 minutes, thevolatiles were removed under vacuum. The residue was extracted withhexane, and filtered through Celite. The hexane was stripped undervacuum to afford a brown liquid, which was identified by ¹H and ¹³C NMRspectroscopy. The yield was 7.6 g.

Synthesis of meso-[dimethylsilylbis(1-indenyl)]hafnium dimethyl(Catalyst I)

The meso dimethyl hafnium compound can be obtained from the racemichafiium dichloride according to the following procedure.Rac-dimethylsilylbis(indenyl)hafnium dichloride was purchased fromBoulder Scientific Co. In an inert atmosphere drybox, 1.002 g ofrac-dimethylsilylbis(indenyl)hafnium dichloride was dissolved inapproximately 30 mL of dry THF. To this solution was added with stirnng1.3 mL of CH₃MgCl (3.0 M in ThF, Aldrich) via syringe. The solutionturned slightly darker and was allowed to stir at room temperature for45 minutes. The THF was subsequently removed under vacuum. The residuewas dissolved in hot methylcyclohexane, filtered through Celite, andcooled. Small crystals immediately formed upon cooling. The solution wasre-warmed, and allowed to cool slowly. The crystalline product wascollected by filtration and characterized by ¹H and ¹³C NMRspectroscopy, as well as single-crystal X-ray diffraction.

Synthesis of Armeenium Borate [methylbis(hydrogenatedtallowalkyl)Ammonium Tetrakis (Dentafluoro phenyl) borate]

Armeenium borate can be prepared from ARMEEN® M2HT (available fromAkzo-Nobel), HCl, and Li [B(C₆ ₅)₄] according to Example 2 of U.S. Pat.No. 5,919,983, the entire disclosure of which is herein incorporated byreference.

Preparation of Antioxidant/Stabilizer Additive Solution:

The additive solution was prepared by dissolving 6.66 g of Irgaphos 168and 3.33 g of Irganox 1010 in 500 mL of toluene. The concentration ofthis solution is therefore 20 mg of total additive per 1 mL of solution.

General Procedure for Determining R_(v) and Comonomer Incorporation

Solution semi-batch reactor copolymerizations of ethylene and octene arecarried out in a 1 gallon metal autoclave reactor equipped with amechanical stirrer, a jacket with circulating heat transfer fluid, whichcan be heated or cooled in order to control the internal reactortemperature, an internal thermocouple, pressure transducer, with acontrol computer and several inlet and output valves. Pressure andtemperature are continuously monitored during the polymerizationreaction. Measured amounts of 1-octene are added to the reactorcontaining about 1442 g Isopar E as solvent. The reactor is heated up tothe reaction temperature with stirring (typically about 1,000 rpm orhigher) and then pressurized with ethylene at the desired pressure untilthe solvent is saturated. The active catalyst is prepared in a drybox bysyringing together solutions of the appropriate catalyst, cocatalyst,and any scavenger (if desired) components with additional solvent togive a total volume which can be conveniently added to the reactor(typically 10-20 mL total). If desired, a portion of the scavenger(typically an aluminum alky, alumoxane, or other alkyl-aluminumcompound) may be added to the reactor separately prior to the additionon the active catalyst solution. The active catalyst solution is thentransferred by syringe to a catalyst addition loop and injected into thereactor over approximately 4 minutes using a flow of high pressuresolvent. The polymerization is allowed to proceed for the desired lengthof time while feeding ethylene on demand to maintainsa constantpressure. The amount of ethylene consumed during the reaction ismonitored using a mass flowmeter. Immediately following the desiredpolymerization time, the polymer solution is then dumped from thereactor using a bottom-valve through a heated transfer line into anitrogen-purged glass kettle containing 10-20 mL of isopropanol, whichacts as a catalyst kill. An aliquot of the additive solution describedabove is added to this kettle and the solution stirred thoroughly (theamount of additive used is chosen based on the total ethylene consumedduring the polymerization, and is typically targeted at a level of about1000-2000 ppm). The polymer solution is dumped into a tray, air driedovernight, then thoroughly dried in a vacuum oven for two days. Theweights of the polymers are recorded and the efficiency calculated asgrams of polymer per gram of transition metal. Because thepolymerization of ethylene and alpha olefins is quite exothermic, thereis usually an increase in the temperature (an exotherm) of the reactionsolution which is observed after the active catalyst is added. Theprocess control computer can be used to keep the reaction temperaturerelatively constant during the polymerization reaction by cooling thejacket of the reactor, but some deviation from the set point is usuallyobserved, especially for catalysts having a relatively fast initial rateof polymerization. If too much active catalyst is added to thesemi-batch reactor, the exotherm can be quite large, and the monomerconcentrations, especially the ethylene concentration, can deviatesignificantly from the equilibrium concentration. Because the polymermolecular weight and the comonomer incorporation depend significantly onthe ethylene concentration, it is important to control the exotherm. Forthe semi-batch reactor polymerizations reported herein, the exotherrnwas generally kept below 5° C. or less. Various catalysts differsignificantly in their rates of polymerization and thus, the amount ofexotherm. The exotherm can be controlled by adjusting the amount or rateof addition of the catalyst.

Using the general solution semi-batch reactor polymerization proceduredescribed above, 17 g of 1-octene was added along with 1455 g ofISOPAR-E. This was heated to 160° C., and saturated with ethylene atabout 166 psi total reactor pressure. A catalyst solution was preparedby combining solutions of selected Catalyst precursor, Anneenium borate,and MMAO-3A to give 5 pimoles of metal, 6.5 Emoles of Armeenium borate,and 25 μmoles of A1. The catalyst solution was added to the reactor asdescribed in the general procedure. After 10 minutes reaction time, thebottom valve was opened and the reactor contents transferred to theglass kettle containing isopropanol. The additive solution was added andthe polymer solution was stirred to mix well. The contents were pouredinto a glass pan, cooled and allowed to stand in a hood overnight, anddried in a vacuum oven for 2 days.

One method to quantify and identify unsaturation in ethylene-octeneCopolymers is ¹H NMR. The sensitivity of ¹H NMR spectroscopy is enhancedby utilizing the technique of peak suppression to eliminate large protonsignals from the polyethylene back bone. This allows for a detectionlimit in the parts per million range in approximately one hour dataacquisition time. This is in part achieved by a 100,000-fold reductionofthe signal from the —CH₂— protons which in turn allows for the data tobe collected using a higher signal gain value. As a result, theunsaturated end groups can be rapidly and accurately quantified for highmolecular weight polymers.

The samples were prepared by adding approximately 0.100 g of polymer in2.5 ml of solvent in a 10 mm NMR tube. The solvent is a 50/50 mixture of1,1,2,2-tetrachloroethane-d2 and perchloroethylene. The samples weredissolved and homogenized by heating and vortexing the tube and itscontents at 130° C. The data was collected using a Varian Unity Plus 400MHz NMR spectrometer. The acquisition parameters used for the Presatexperiment include a pulse width of 30 us, 200 transients per data file,a 1.6 sec acquisition time, a spectral width of 10000 Hz, a file size of32K data points, temperature setpoint 110° C., D1 delay time 4.40 sec,Satdly 4.0 sec, and a Satpwr of 16.

Comonomer content was measured by ¹³C NMR Analysis. The samples wereprepared by adding approximately 3 g of a 50/50 mixture oftetrachloroethane-d2/orthodichlorobenzene to 0.4 g sample in a 10 mm NMRtube. The samples were dissolved and homogenized by heating the tube andits contents to 150° C. The data was collected using a JEOL Eclipse 400MHz NMR or Varian Unity Plus 400 MHz spectrometer, corresponding to a¹³C resonance frequency of 100.4 MHz. The data was acquired using NOE,1000 transients per data file, a 2 sec pulse repetition delay, spectralwidth of 24,200 Hz and a file size of 32K data points, with the probehead heated to 130° C.

The various amounts of unsaturations and comonomer incoporation bydifferent. catalysts preparaed by the above-described semi-batchprocedure were calculated. Values for the R_(v), and the1-octene-incorporation of exemplary catalysts obtained by these methodsare recorded in Table IV. TABLE IV Catalyst Properties Mole % CatalystR_(v) 1-octene M_(w) A (N-(1,1-dimethylethyl)-1,1-di-(4-nbutylphenyl)-1-0.20 2.62 196,000 ((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium Brac-[1,2-ethanediylbis(1-indenyl)]zirconium (1,4-diphenyl- 0.44 0.6419,200 1,3-butadiene) C (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) 0.172.01 82,000 D dimethylsilyl(2-methyl-s-indacenyl)(t-butylamido) 0.232.28 119,400 titanium 1,3-pentadiene E[(3-Phenylindenyl]SiMe2NtBut]TiMe2 0.39 2.01 85,700 Fdimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden- 0.34 3.33 44,0001-yl)zirconium η⁴-1,4-diphenyl-1,3-butadiene G(N(-1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,9a,-h)- 0.44 2.97105,000 5,6,7,8-tetrahydro-3-phenyl-5,5,8,8-tetramethyl-1H-benz(f)inden-1-yl)silanaminato(2-)N)dimethyltitanium Hbis(n-butylcyclopentadienyl)zirconium dimethyl 0.16 0.3 10,000 Imeso-[dimethylsilylbis(1-indenyl)]hafnium dimethyl 0.07 1.11 21,600

General 1 Gallon Continuous Solution Ethylene Polymerization Procedure

Purified ISOPAR-E solvent, ethylene, and hydrogen are supplied to a 1Liter reactor equipped with a jacket for temperature control and aninternal thermocouple. The solvent feed to the reactor is measured by amass-flow controller. A variable speed diaphragm pump controls thesolvent flow rate and increases the solvent pressure to the reactor. Thecatalyst feeds are mixed with the solvent stream at the suction of thesolvent pump and are pumped to the reactor with the solvent. Thecocatalyst feed is added to the monomer stream and continuously fed tothe reactor separate from the catalyst stream. The ethylene stream ismeasured with a mass flow meter and controlled with a Research Controlvalve. A mass flow controller is used to deliver hydrogen into theethylene stream at the outlet of the ethylene control valve. Thetemperature of the solvent/monomer is controlled by use of a heatexchanger before entering the reactor. This stream enters the bottom ofthe reactor. The catalyst component solutions are metered using pumpsand mass flow meters, and are combined with the catalyst flush solvent.This stream enters the bottom of the reactor, but in a different portthan the monomer stream. The reactor is run liquid-full at 450 psig withvigorous stirring. The process flow is in from the bottom and. out ofthe top. All exit lines from the reactor are steam traced and insulated.Polymerization is stopped with the addition of a small amount of water,and other additives and stabilizers can be added at this point. Thestream flows through a static mixer and a heat exchanger in order toheat the solvent/polymer mixture. The solvent and unreacted monomer areremoved at reduced pressure, and the product is recovered by extrusionusing a devolatilizing extruder. The extruded strand is cooled underwater and chopped into pellets. The operation of the reactor iscontrolled with a process control computer.

Example 1 Ethylene Polymerization with Catalysts A and B

Using the general continuous solution polymerization procedure describedabove, ethylene and ISOPAR-E solvent were fed into the reactor at ratesof about 4.50 lbs/hour and 26.50 lbs/hour, respectively. The temperaturewas maintained at about 140° C., and saturated. The polymer of Example 1was prepared by feeding Catalyst A and Catalyst B, Armeenium borate, andMMAO-3A to the reactor to produce a catalyst concentration of 1.2 ppm, aratio of catalyst A to catalyst B of 0.34, 22.8 ppm of Armeenium borate,and 4.3 ppm of A1 according to the general procedure. The polymer ofExample 2 was prepared by feeding Catalyst A and Catalyst B, Armeeniumborate, and MMAO-3A to the reactor to produce a catalyst concentrationof 0.60 ppm, a ratio of catalyst A to catalyst B of 0.33, 7.6 ppm ofArmeenium borate, and 4.3 ppm of A1 according to the general procedure.Other process parameters are recorded in Table I.

Examples 2-11 Ethylene Polymerization with Catalysts A and B

The general procedure for continuous solution polymerization describedabove was repeated for Examples 2-9. Various parameters of the reactionare recorded in Table I.

Examples 11-13 Ethylene/1-Octene Interpolymers using Catalysts A and B

Ethylene/1-Octene interpolymers were prepared using the general.continuous solution procedure described above. Ethylene, 1-octene, andISOPAR-E solvent were fed into the reactor at rates of about 4.50lbs/hour, 0.70 lbs/hour, and 30.20 lbs/hour, respectively. Thetemperature was maintained at about 140° C., and saturated. Examples 3and 4 were prepared by feeding Catalyst A and Catalyst B, Armeeniumborate, and MMAO-3A to the reactor to produce a catalyst concentrationof 2.36 ppm, a ratio of catalyst A to catalyst B of 0.44, 53.2 ppm ofArmeenium borate, and 8.6 ppm of A1 according to the general procedure.Other process parameters are also recorded in Table V. TABLE VPolymerization conditions and properties of resulting polymer ethylenesolvent, flow, octene flow, H₂ flow, ethylene Example temperature, C.flow, lb./hr lb/hr lb/hr sccm conversion, % 1 140.3 4.50 22.6 0.00 50.090.23 2 139.0 4.50 26.5 0.00 5.0 90.08 3 140.2 4.50 29.2 0.00 0.0 90.204 138.5 4.50 31.0 0.00 4.1 94.88 5 140.2 4.50 31.0 0.00 4.7 94.88 6139.8 4.50 31.0 0.00 6.9 95.15 7 140.9 4.50 31.0 0.00 99.9 97.67 8 140.74.50 31.0 0.00 75.0 98.57 9 140.8 4.50 31.0 0.00 64.9 98.53 10 141.04.50 26.50 0.00 0.00 90.23 11 140.7 4.50 26.50 0.00 0.00 90.19 12 130.34.50 30.20 0.70 0.00 89.97 13 130.9 4.50 30.20 0.70 0.00 90.28 ppm metalefficiency, polymer Cat A/ g/g production density, Example Cat B metalrate, lb/hr g/mL I₂ I₁₀/I₂ 1 0.65/0.35 14,900,000 4 0.9638 — — 20.65/0.35 20,300,000 4 0.9609 — — 3 0.65/0.35 20,500,000 4 0.9616 — — 40.65/0.35 9,500,000 4 0.9561 — — 5 0.65/0.35 9,500,000 4 0.9594 — — 60.65/0.35 9,500,000 4 0.9582 — — 7 13.52/2.48  500,000 4 0.9579 — — 813.52/2.48  600,000 4 0.9539 — — 9 13.52/2.48  600,000 4 0.9537 — — 100.31/0.90 30,900,000 4 0.9643 9.17 8.66 11 0.15/0.45 34,000,000 4 0.964310.86 8.43 12 0.72/1.64 4,500,000 4 0.9432 1.31 16.34 13 0.72/1.644,500,000 4 0.9431 0.97 16.24 Wt % ppm H₂ of Example Wt % ethylenepolymer reactor feed Mw Mn MWD 1 100 — — 94,500 12,200 7.75 2 100 — —170,400 24200 7.04 3 100 — — 189,900 18,700 10.16 4 100 — — 186,40021,600 8.63 5 100 — — 149,800 20,500 7.31 6 100 — — 159,500 13,900 11.477 100 — — 71,700 8750 8.19 8 100 — — 87,000 15,400 5.65 9 100 — — 99,60016,000 6.23 10 100 — — 56,700 18,900 3.00 11 100 — — 54,300 36,100 2.8912 97.4 — — 112,200 35,100 5.61 13 97.2 — — 115,100 35,600 5.40

The GPC traces of the polymers of Examples 14 were deconvoluted toresolve the contribution of the high molecular weight component and thelow molecular weight component. FIG. 2 shows the molecular weightdistribution and the deconvoluted solutions from the high molecularweight component and the low molecular weight component for the polymerof Example 2. The results of the deconvolutions for Examples 1-13 arecollected in Table VI. TABLE VI Deconvoluted Polymer Properties M_(w) ofHigh M_(n) of High MWD of M_(w) of Low M_(n) of Low MWD of MW MW High MWMW MW Low MW Example Split Fraction Fraction Fraction Fraction FractionFraction M_(w) ^(H)/M_(w) ^(L) 1 0.28 291708 136383 2.14 32,517 137902.36 8.98 2 0.20 606850 297850 2.04 39,335 17816 2.21 15.43 3 0.24743170 365057 2.04 38817 17897 2.17 19.15 4 0.30 578758 283139 2.0439415 17713 2.23 14.68 5 0.23 575660 285589 2.02 40421 17785 2.27 14.246 0.28 540461 266306 2.03 39871 17603 2.27 13.56 7 0.72 110248 450762.45 15566 6301 2.47 7.08 8 0.86 99920 41537 2.41 11688 4734 2.47 8.55 90.74 137167 56167 2.44 17418 7049 2.47 7.88 10 0.03 663,868 268,196 2.4840,908 18,409 2.22 16.22 11 0.03 555,572 273,900 2.03 40,669 18,298 2.2213.66 12 0.12 691,422 345,719 2.00 38,821 18,292 2.12 17.81 13 0.13659,512 327,888 2.01 38,981 18,279 2.13 16.91

The polymers from Examples 1-13 were characterized by numeroustechniques. Table VII summarizes the physical properties of the polymersof Examples 10-13 obtained in this study. Also included in Table VII forcomparison are data for LDPE 682I and LDPE 170A, which are commercialfree-radical LDPE resins available from The Dow Chemical Company. TABLEVII Polymer Characterization Data LDPE LDPE Resin Example 1 Example 2Example 3 Example 4 682I 170A Density grams/cc 0.9643 0.9643 0.94320.9431 0.9211 0.9225 I₅ 27.99 29.60 5.74 4.27 2.38 2.96 I₁₀ g/10 min79.47 91.54 21.40 15.75 8.25 9.86 I₂ g/10 min 9.17 10.86 1.31 0.970.6923 0.5643 I_(10/I) ₂ — 8.66 8.43 16.34 16.24 11.9 17.5 GPC Data Mw —56,700 54,300 112,200 115,100 84,000 91,700 Mp — 35600 36100 35100 3560061,300 56,500 Mn — 18,900 36,100 35,100 35,600 25,300 17,000 Mw/Mn —3.00 2.89 5.61 5.40 3.32 5.39 Melt Strength cN 7 7 33 36 18 16The melt strength as a finction of the melt index is illustrated in FIG.3. As FIG. 3 suggests some interpolymers have melt strengths thatindicate a higher bubble stability for film fabrication and improvedblow molding.

Examples 14-19 5 Gallon Continuous Polymerization of Ethylene

The general procedure described above for the 1 Gallon continuouspolymerization of ethylene was applied to a larger 5 gallon continuouspolymerization reactor. Two catalyst solutions containing 5 ppm ofCatalyst A and 10 ppm of catalyst B, respectively, were prepared andadded to separate 4 L catalyst storage tanks. These two solutions werefed at a controlled rate and combined in a continuous stream with acontinuous stream of ISOPAR-E solvent along with a continuous stream ofMMAO-3A to give a molar ratio of catalyst:metals:A1 of 1:5. The catalystsolution was fed continuously into the reactor at a rate sufficient.tomaintain the reactor temperature at approximately 140° C. and anethylene conversion of about 92%. The Armeenium borate cocatalystsolution was mixed with the monomer feed and added separately andcontinuously fed as an ISOPAR-E solution having a molar ratio ofboron:metal of 1.1:1. The production rate for each example wasapproximately 3.8 Kr/Hour. For each example, the hydrogen feed andcatalyst mixture were adjusted to produce an a product having a meltindex (I₂) of approximately 1.0. Details for the reactor conditions arerecorded in Table VIII.

The polymer solution was continuously removed from the reactor exit andwas. contacted with a solution containing 100 ppm of water for each partof the polymer solution, and polymer stabilizers. The resulting exitstream was mixed, heated in a heat exchanger, and the mixture wasintroduced into a separator where the molten polymer was separated fromthe solvent and unreacted monomers. The resulting molten polymer wasextruded and chopped into pellets after being cooled in a water bath.Product samples were collected over 1 hour time periods, after whichtime the melt index and density was determined for each sample. The meltstrength and melt index of the resulting polymers were measured and arealso reported in Table VIII. TABLE VIII Process Conditions and PolymerProperties for Examples 14-19 Melt Strength Solv Ethyl H₂ Temp CatalystB Catalyst A Conv I₂ Velocity Example kg/hr kg/hr sml/min ° C. gr/hrgr/hr % Force (cN) mm/s 14 32 4.34 0 143 27 135 91.5 0.97 28 41.6 15 323.8 19 140 50 45 90 1.27 19 60.8 16 34 3.8 38 140 50 50 92 1.05 13 89.417 34 3.8 38 140 50 50 92 0.80 13 77.4 18 34 3.8 54 141 55 67 91.5 0.999 134.3 19 34 3.8 54 141 55 69 92 0.82 9 73.2

FIG. 2 plots the melt strength data for ethylene interpolymers ofExamples 14 and 14-19, as well as for LDPE 682I as a function of themelt index (I₂).

As demonstrated above, embodiments of the invention provide a newprocess for making olefin polymers. The novel process may offer one ormore of the following advantages. First, the costs associated with thisprocess are similar to those for metallocene catalyzed processes. Goodcatalyst efficiency is obtained in such a process. The processability ofthe polymer produced by the process is often better than that of ametallocene catalyzed polymer produced with a single catalyst.Therefore, it is now possible to produce an interpolymer with betterprocessability without sacrificing efficiency and thus incurring highercosts. Because at least two catalysts are used in the polymerizationprocess, it is possible to adjust the density split and the polymersplit by selecting the proper catalysts, if desired. By controlling thedensity split and/or the polymer split, one may design a series ofpolymers with desired characteristics and properties. With such aprocess, it is possible to adjust the density split and the polymersplit from 0 to 100%. By proper selection of catalysts, it is alsopossible to increase the level of long chain branching substantially.Moreover, a comb-like long chain branching structure is obtained.

The polymers in accordance with embodiments of the invention may offerone or more of the following advantages. First, the processability andoptical properties of certain of the interpolymers are similar to LDPE,while the mechanical properties of certain of the interpolymers arebetter than LDPE. Moreover, the improved processability is not obtainedat the expense of excessive broadening of the molecular weightdistribution. The interpolymers also retain many of the desiredcharacteristics and properties of a metallocene catalyzed polymer. Inessence, some polymers prepared in accordance with embodiments of theinvention combine the desired attributes of LDPE and metallocenecatalyzed polymers. Some polymers have higher melt strength than LDPEsat the same molecular weight. Additional advantages are apparent tothose skilled in the art.

While the invention has been described with a limited number ofembodiments, these specific embodiments are not intended to limit thescope of the invention as otherwise described and claimed herein.Modification and variations from the described embodiinents exist. Forexample, while the high molecular weight catalysts and the low molecularweight catalysts are described with reference to a single site ormetallocene catalyst, suitable catalysts are not so limited. It ispossible to combine a Ziegler-Natta catalyst with a single site ormetallocene catalyst, provided that the catalyst meet the selectioncriteria for producing a desired polymer. A person of ordinary skill inthe art recognizes that catalyst activities may vary, depending on thetemperature, pressure, monomer concentration, polymer concentration,hydrogen partial pressure and so on. It should also be recognized thatco-catalysts may impact the catalyst's ability to produce interpolymersand the capability to incorporate comonomers. Therefore, one pair ofcatalysts which does not fulfill the selection criteria under one set ofreaction conditions may nevertheless be used in embodiments of theinvention under another set ofreaction conditions. While all of theembodiments are described with reference to a pair of catalysts, it byno means precludes the use of three, four, five, or more catalystssimultaneously in a single reactor with similar or different capabilityfor molecular weight and/or cbmonomer incorporation. Although theprocess is described with reference to the production of interpolymers,homopolymers, such as homopolyethylene, homopolypropylene,homopolybutylene, etc. may also be produced by the process describedherein. These homopolymers are expected to have a high level of longchain branching and thus exhibit improved processability whilemaintaining the desired characteristics possessed by the homopolymersproduced by one metallocene catalyst. It should be recognized that theprocess described herein may be used to make terpolymers, tetrapolymers,or polymers with five or more comonomers. The incorporation ofadditional comonomers may result in beneficial properties which are notavailable to copolymers. While the processes are described as comprisingone or more steps, it should be understood that these steps may bepracticed in any order or sequence unless otherwise indicated. Thesesteps may be combined or separated. Finally, any number disclosed hereinshould be construed to mean approximate, regardless of whether the word“about” or “approximate” is used in describing the number. The appendedclaims intend to cover all such variations and modifications as fallingwithin the scope of the invention.

1-59. are cancelled.
 60. A process of making a polymer, comprising: a)contacting one or more olefinic monomers in the presence of at least ahigh molecular weight (HMW) catalyst and at least a low molecular weight(LMW) catalyst in a polymerization reactor system; and b) effectuatingthe polymerization of the one or more olefinic monomers in thepolymerization reactor system to obtain an olefin polymer, wherein theLMW catalyst has an R_(v) ^(L), defined as$R_{v}^{L} = \frac{\text{[vinyl]}}{\text{[vinyl]} + \text{[vinylidene]} + \text{[cis]} + \text{[trans]}}$wherein [vinyl] is the concentration of vinyl groups in the olefinpolymer produced by the low molecular weight catalyst expressed invinyls/1,000 carbon atoms; [vinylidene], [cis] and [trans] are theconcentration of vinylidene, cis and trans groups in the olefin polymerexpressed in the number of the respective groups per 1,000 carbon atoms,of greater than 0.12, and wherein the HMW catalyst has a reactivityratio, r1 of about 5 or less.
 61. The process of claim 60, wherein anR_(v) ^(H) for the high molecular weight catalyst is defined as$R_{v}^{H} = \frac{\text{[vinyl]}}{\text{[vinyl]} + \text{[vinylidene]} + \text{[cis]} + \text{[trans]}}$wherein [vinyl] is the concentration of vinyl groups in the olefinpolymer produced by the low molecular weight catalyst expressed invinyls/1,000 carbon atoms; [vinylidene], [cis] and [trans] are theconcentration of vinylidene, cis and trans groups in the olefin polymerexpressed in the number of the respective groups per 1,000 carbon atoms,and wherein a ratio of R_(v) ^(L)/R_(v) ^(H) ranges from 0.5 to about2.0.
 62. The process of claim 60, wherein R_(v) ^(L) is greater than0.15.
 63. The process of claim 60, wherein R_(v) ^(L) is greater than0.20.
 64. The process of claim 60, wherein R_(v) ^(L) is greater than0.25.
 65. The process of claim 60, wherein R_(v) ^(L) is greater than0.35.
 66. The process of claim 60, wherein R_(v) ^(L) is greater than0.45.
 67. The process of claim 60, wherein R_(v) ^(L) is greater than0.50.
 68. The process of claim 60, wherein r₁ is about 4 or less. 69.The process of claim 60, wherein r₁ is about 3 or less.
 70. The processof claim 61, wherein the R_(v) ^(L)/R^(H) ratio is about 0.80 to about1.40.
 71. The process of claim 60, wherein the high molecular weightcatalyst or the low molecular weight catalyst are supported on an inertsupport.
 72. The process of claim 60, wherein the polymerization reactorsystem includes a first reactor connected to a second reactor inparallel so that mixing occurs in a third reactor.
 73. The process ofclaim 72, wherein the HMW catalyst contacts the one or more olefinmonomers in the first reactor to produce a first reactor product and theLMW catalyst contacts the first reactor product in the second reactor.74. The process of claim 60, wherein the first reactor is connected tothe second reactor in series and the HMW catalyst contacts the one ormore olefin monomers in the first reactor to produce a first reactorproduct and the LMW catalyst contacts the first reactor product in thesecond reactor.
 75. The process of claim 72, wherein the HMW catalyst,the LMW catalyst, and the one or more olefinic monomers are sequentiallyintroduced into the polymerization reactor system.
 76. The process ofclaim 60, wherein the process is operated under continuous solutionpolymerization conditions.
 77. The process of claim 60 wherein theprocess is a slurry process.
 78. The process of claim 60, wherein thefirst reactor is operated under gas-phase polymerization conditions.